CN111036243B - Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof - Google Patents
Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001301 oxygen Substances 0.000 title claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 50
- 239000002135 nanosheet Substances 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000007704 transition Effects 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
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- 150000003624 transition metals Chemical class 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- UGNANEGDDBXEAS-UHFFFAOYSA-L nickel(2+);dichloride;dihydrate Chemical compound O.O.Cl[Ni]Cl UGNANEGDDBXEAS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 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 19
- 239000002244 precipitate Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 43
- 229910052742 iron Inorganic materials 0.000 abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011733 molybdenum Substances 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 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 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000015393 sodium molybdate Nutrition 0.000 abstract 1
- 239000011684 sodium molybdate Substances 0.000 abstract 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002055 nanoplate Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000002019 doping agent Substances 0.000 description 9
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- 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
Abstract
The invention discloses a BiOBr nanosheet photocatalyst doped with oxygen-containing vacant transition metals (iron, molybdenum and nickel), a preparation method thereof and application of the BiOBr nanosheet photocatalyst in producing ammonia by photocatalytic reduction of nitrogen. Bismuth nitrate pentahydrate, potassium bromide and metal salts (anhydrous ferric chloride, sodium molybdate and nickel chloride dihydrate) are used as raw materials, a transition metal doped BiOBr nanosheet is synthesized by a hydrothermal method, and the oxygen-containing vacancy transition metal doped BiOBr nanosheet photocatalyst is obtained by secondary solvothermal treatment. The method has simple preparation process, takes visible light as driving energy and water as a reaction solvent, uses the oxygen-vacancy-containing transition metal-doped BiOBr nanosheet for photocatalytic reduction of nitrogen to produce ammonia for the first time, has high catalytic activity, and is beneficial to sustainable development of environment and energy.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and sustainable development of environment and energy, and particularly relates to an oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst as well as a preparation method and application thereof.
Background
Nitrogen is a major component of the atmosphere and is readily available in nature. It contains nitrogen as an essential element for all biological construction of proteins and other biomolecules. The problem of achieving efficient nitrogen utilization has long been a serious challenge, since inert N ≡ N bonds possess extremely strong bond energy and are difficult to break. Currently, the conversion of nitrogen to ammonia is industrially carried out mainly by the Haber-Bosch process, which reduces nitrogen in air and hydrogen in methane vapor to ammonia at high temperature (673-873K) and strong pressure (15-25 MPa). However, this operation consumes a large amount of fossil fuel and is not environmentally friendly. In contrast, the photocatalytic nitrogen conversion technology, as a green technology, takes solar energy as a driving force and water as a hydrogen source, provides a promising alternative for the future application of the haber-bosch process.
The BiOBr nano sheet is a ternary two-dimensional nano material. The photocatalyst has response under visible light, chemical stability and low toxicity, so that the photocatalyst has great attention on the aspect of photocatalytic nitrogen fixation. However, the BiOBr material is difficult to adsorb and activate inert nitrogen molecules, so that the popularization and application of the BiOBr material in the field of converting nitrogen into ammonia are severely restricted. The heteroatom doping can provide nitrogen absorption and activation sites for the catalyst, and can make up for the defect that the BiOBr material cannot effectively adsorb nitrogen. So far, iron (Fe) element and molybdenum (Mo) element have attracted much attention as key elements for nitrogen fixation as active sites in nitrogen-fixing bacteria, an effective nitrogen-fixing substance in the biological world. In addition, the transition metal nickel (Ni) has also proven to have some success in nitrogen fixation. Therefore, if transition metals (iron, molybdenum and nickel) are introduced into the BiOBr semiconductor material for photocatalytic nitrogen fixation, the method has profound significance and broad prospects in the fields of material synthesis and photocatalytic nitrogen fixation.
Disclosure of Invention
The invention aims to provide a preparation method of a BiOBr nanosheet photocatalyst doped with transition metals (iron, molybdenum and nickel) with oxygen vacancies, which has the advantages of high photocatalytic activity, low manufacturing cost, simple production process, macroscopic preparation, environmental friendliness and application of the BiOBr nanosheet photocatalyst in photocatalytic reduction of nitrogen in aqueous phase under visible light.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst comprises the following steps:
(1) preparing a transition metal (iron, molybdenum and nickel) doped BiOBr nanosheet by a hydrothermal method:
adding a transition metal salt solution (ferric chloride or ammonium molybdate or nickel chloride dihydrate) into a nitric acid solution containing bismuth nitrate, stirring for ten minutes, dropwise adding a potassium bromide solution into the solution, uniformly mixing, adjusting the pH value of the mixed solution to be neutral by using ammonia water, and adding the solution into a Teflon-lined stainless steel autoclave with the capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. Drying the final product in a 333K oven for 12 hours to obtain a transition metal doped BiOBr nano sheet without oxygen vacancy;
(2) preparing a BiOBr nanosheet photocatalyst doped with oxygen-containing vacant transition metals (iron, molybdenum and nickel) by a solvothermal method:
ultrasonically dispersing the BiOBr nano sheet prepared in the step (1) into ethylene glycol to prepare a solution with the concentration of 19 g/L, stirring for one hour, and adding the solution into a Teflon-lined stainless steel autoclave with the capacity of 25 mL for secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. And drying the final product in a vacuum oven for 12 hours to obtain the oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst.
Further, in the step (1), the concentration of the bismuth nitrate in the nitric acid solution containing the bismuth nitrate is 48.5 g/L, and the concentration of the nitric acid is 63 g/L; the concentration of the potassium bromide is 23.8 g/L; the concentration of the transition metal salt is 0.08M; the volume ratio of the potassium bromide solution to the nitric acid solution containing bismuth nitrate is 1: 2; the molar ratio of the transition metal salt to the bismuth nitrate is 0.5-3%.
The oxygen-vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst can catalyze nitrogen to reduce under the irradiation of visible light to generate ammonia, and the specific operation steps are as follows:
(1) taking a certain amount of ultrapure water and a BiOBr nanosheet photocatalyst doped with oxygen-containing vacancy transition metal into a reaction bottle, ultrasonically homogenizing, introducing nitrogen (30 mL/min) while stirring, adsorbing for 30 minutes in a dark state, and enabling the nitrogen to reach adsorption balance on the surface of the photocatalyst;
(2) the system was illuminated under continuous nitrogen bubbling (30 mL/min) for 2 hours, after the reaction was complete, centrifuged, the catalyst was recovered, and the liquid was analyzed by UV-visible absorption spectroscopy.
Under the irradiation of visible light, oxygen vacancies in the photocatalyst can expose transition metal (iron, molybdenum and nickel) dopants, the transition metal dopants can be used as active sites to effectively adsorb nitrogen, and photo-generated electrons generated by the BiOBr nanosheets can be effectively transferred to the adsorbed nitrogen to effectively catalyze the half reaction of reduction. In addition, the invention also has the following advantages:
(1) the invention introduces transition metal and oxygen vacancy into the BiOBr nano sheet simultaneously, has higher catalytic efficiency and is beneficial to the sustainable development of environment and energy.
(2) The oxygen vacancy-containing transition metal-doped BiOBr photocatalyst has high photocatalytic activity, low manufacturing cost, simple production process, macroscopic preparation, environmental friendliness and easy recovery.
Drawings
Fig. 1 is a scanning electron micrograph and a transmission electron micrograph of different materials, wherein (a) is an SEM image of the BiOBr nanoplates prepared in example 1; (B) SEM image of transition metal iron doped BiOBr nanoplates prepared in example 2; (C) SEM image of oxygen-containing vacancy bibbr nanoplates prepared for example 6; (D) high resolution TEM images of oxygen vacancy-containing transition metal iron-doped BiOBr nanoplates prepared in example 8;
FIG. 2 is an X-ray diffraction pattern of different materials;
FIG. 3 is a graph of the UV-VIS diffuse reflectance spectra of various materials;
fig. 4 is a graph of the activity of different metals of iron (a), molybdenum (B), and nickel (C) doped oxygen-free and oxygen-containing vacancy of the BiOBr nanosheet photocatalyst for visible light reduction of nitrogen.
Detailed Description
Example 1 preparation of BiOBr nanoplates:
23.8 g/L of potassium bromide solution was added dropwise to 48.5 g/L of bismuth nitrate solution in nitric acid at a volume ratio of 1:2, the mixture was mixed well, the pH of the mixed solution was adjusted to neutral with ammonia water, and the solution was charged into a Teflon-lined stainless steel autoclave having a capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. The final product was dried in a 333K oven for 12 hours. Obtaining the BiOBr nano sheet.
Example 2 preparation of transition metal (iron, molybdenum, or nickel) doped BiOBr nanoplates:
a solution of 0.08M ferric chloride or ammonium molybdate or nickel chloride dihydrate was added to a 48.5 g/L nitric acid solution of bismuth nitrate and stirred for ten minutes (molar ratio of transition metal salt to bismuth nitrate was 0.5%). According to the volume ratio of 1: 2A potassium bromide solution (23.8 g/L) was added dropwise to the above solution, and after mixing uniformly, the pH of the mixed solution was adjusted to neutral with aqueous ammonia, and the solution was charged into a Teflon-lined stainless steel autoclave having a capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. The final product was dried in a 333K oven for 12 hours to yield an oxygen vacancy free transition metal doped BiOBr catalyst product BiOBr-M-0.5 (M = Fe, Mo or Ni).
Example 3 preparation of transition metal (iron, molybdenum, or nickel) doped BiOBr nanoplates:
a solution of 0.08M ferric chloride or ammonium molybdate or nickel chloride dihydrate was added to a 48.5 g/L nitric acid solution of bismuth nitrate and stirred for ten minutes (molar ratio of metal salt to bismuth nitrate was 1%). According to the volume ratio of 1: 2A potassium bromide solution (23.8 g/L) was added dropwise to the above solution, and after mixing uniformly, the pH of the mixed solution was adjusted to neutral with aqueous ammonia, and the solution was charged into a Teflon-lined stainless steel autoclave having a capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. The final product was dried in a 333K oven for 12 hours to yield an oxygen vacancy free transition metal doped BiOBr catalyst product BiOBr-M-1, (M = Fe/Mo/Ni).
Example 4 preparation of transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
a solution of 0.08M ferric chloride or ammonium molybdate or nickel chloride dihydrate was added to a 48.5 g/L nitric acid solution of bismuth nitrate and stirred for ten minutes (molar ratio of metal salt to bismuth nitrate was 2%). According to the volume ratio of 1: 2A potassium bromide solution (23.8 g/L) was added dropwise to the above solution, and after mixing uniformly, the pH of the mixed solution was adjusted to neutral with aqueous ammonia, and the solution was charged into a Teflon-lined stainless steel autoclave having a capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. The final product was dried in a 333K oven for 12 hours to yield an oxygen vacancy free transition metal doped BiOBr catalyst product BiOBr-M-2, (M = Fe, Mo or Ni).
Example 5 preparation of transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
a solution of 0.08M ferric chloride or ammonium molybdate or nickel chloride dihydrate was added to a 48.5 g/L nitric acid solution of bismuth nitrate and stirred for ten minutes (molar ratio of metal salt to bismuth nitrate was 3%). According to the volume ratio of 1: 2A potassium bromide solution (23.8 g/L) was added dropwise to the above solution, and after mixing uniformly, the pH of the mixed solution was adjusted to neutral with aqueous ammonia, and the solution was charged into a Teflon-lined stainless steel autoclave having a capacity of 100 mL. The autoclave was held at 433K for 18 hours and then cooled to room temperature. The precipitate was collected and washed with absolute ethanol and deionized water to remove organic solvent residues. The final product was dried in a 333K oven for 12 hours to yield an oxygen vacancy free transition metal doped BiOBr catalyst product BiOBr-M-3 (M = Fe, Mo or Ni).
Example 6 preparation of oxygen-containing vacancy bibbr nanoplates:
the BiOBr nanosheets prepared in example 1 were ultrasonically dispersed in ethylene glycol to make a 19 g/L solution, stirred for one hour, added to a Teflon-lined stainless steel autoclave having a capacity of 25 mL, and subjected to secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. And drying the final product in a vacuum oven for 12 hours to obtain an oxygen-containing vacancy BiOBr catalyst product BiOBr-S.
Example 7 preparation of oxygen-vacancy-containing transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
the oxygen vacancy-free transition metal-doped BiOBr nanosheets prepared in example 2 were ultrasonically dispersed into ethylene glycol to make a 19 g/L solution, stirred for one hour, added to a Teflon-lined stainless steel autoclave having a capacity of 25 mL and subjected to secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. The final product was dried in a vacuum oven for 12 hours to give the oxygen vacancy containing transition metal doped BiOBr catalyst product BiOBr-M-S-0.5 (M = Fe, Mo or Ni).
Example 8 preparation of oxygen-vacancy-containing transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
the oxygen vacancy-free transition metal-doped BiOBr nanosheets prepared in example 3 were ultrasonically dispersed into ethylene glycol to make a 19 g/L solution, stirred for one hour, added to a Teflon-lined stainless steel autoclave having a capacity of 25 mL and subjected to secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. The final product was dried in a vacuum oven for 12 hours to give the oxygen vacancy containing transition metal doped BiOBr catalyst product BiOBr-M-S-1 (M = Fe, Mo or Ni).
Example 9 preparation of oxygen-vacancy-containing transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
the oxygen vacancy-free transition metal-doped BiOBr nanosheets prepared in example 4 were ultrasonically dispersed into ethylene glycol to make a 19 g/L solution, stirred for one hour, added to a Teflon-lined stainless steel autoclave having a capacity of 25 mL and subjected to secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. The final product was dried in a vacuum oven for 12 hours to give the oxygen vacancy containing transition metal doped BiOBr catalyst product BiOBr-M-S-2 (M = Fe, Mo or Ni).
Example 10 preparation of oxygen-vacancy-containing transition metal (iron, molybdenum or nickel) doped BiOBr nanoplates:
the oxygen vacancy-free transition metal-doped BiOBr nanosheets prepared in example 5 were ultrasonically dispersed into ethylene glycol to make a 19 g/L solution, stirred for one hour, added to a Teflon-lined stainless steel autoclave having a capacity of 25 mL and subjected to secondary hydrothermal treatment. The autoclave was held at 433K for 12 hours and then cooled to room temperature. The precipitate was collected and washed with anhydrous ethanol to remove organic solvent residues. The final product was dried in a vacuum oven for 12 hours to give the oxygen vacancy containing transition metal doped BiOBr catalyst product BiOBr-M-S-3 (M = Fe, Mo or Ni).
Fig. 1 is SEM and TEM images of different materials, wherein, (a) SEM images of bibbr nanoplates prepared in example 1; (B) SEM image of transition metal iron doped bibbr nanoplates prepared in example 2; (C) SEM image of oxygen vacancy-containing BiOBr nanoplates prepared in example 6; (D) TEM images of oxygen vacancy-containing transition metal iron-doped BiOBr nanoplates prepared in example 8. As can be seen from fig. 1, the BiOBr nanosheet exhibits a good two-dimensional sheet structure; after the introduction of the oxygen vacancy and the metal dopant, the two-dimensional sheet structure of the BiOBr is not obviously changed, which indicates that the introduction of the oxygen vacancy or the metal dopant does not influence the morphological characteristics of the BiOBr; as can be seen from the TEM image of oxygen-vacancy-containing transition metal iron-doped BiOBr nanoplates of fig. D, the synthesized samples had (102) lattice fringes of the BiOBr crystals.
FIG. 2 is an X-ray diffraction pattern of different materials. As can be seen from fig. 2 (a), the introduction of the metal dopant does not affect the crystal structure of the BiOBr; as can be seen from fig. 2 (B), neither the introduction of oxygen vacancies nor the simultaneous introduction of oxygen vacancies and metal dopant affects the crystal structure of the BiOBr.
Fig. 3 is a uv-vis diffuse reflectance spectrum of different materials. As can be seen from fig. 3 (a) and (B), the introduction of oxygen vacancies has no significant effect on the light absorption of the BiOBr; the introduction of the metal dopant can effectively enhance the light absorption of the BiOBr in the visible light range.
Fig. 4 is a graph of the activity of different metals (a) iron, (B) molybdenum, (C) nickel doped oxygen-free and oxygen-containing vacancy bibbr photocatalysts in visible light reduction of nitrogen. Dispersing 10 mg of photocatalyst in 10 mL of ultrapure water by ultrasonic, introducing nitrogen (30 mL/min) for 30 minutes, then placing the solution under visible light (lambda is more than 400 nm) for illumination for 2 hours, and analyzing the reacted liquid by adopting ultraviolet-visible absorption spectroscopy. As can be seen from the figure, the activity of the BiOBr nanosheet only introduced with the metal dopant has no obvious activity difference with that of the single BiOBr nanosheet, and the performance of the BiOBr photocatalyst in reducing nitrogen by visible light can be effectively improved only after the oxygen vacancy and the metal dopant are introduced.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. An oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst, which is characterized in that: the preparation method specifically comprises the following steps:
(1) preparing a transition metal doped BiOBr nanosheet by a hydrothermal method:
adding a transition metal salt solution into a nitric acid solution containing bismuth nitrate, and uniformly stirring; dropwise adding a potassium bromide solution, uniformly mixing, adjusting the pH value of the mixed solution to be neutral by using ammonia water, then adding the mixed solution into an autoclave, keeping the mixed solution at 433K for 18h, cooling to room temperature, collecting precipitate, washing, and drying at 333K for 12h to obtain oxygen vacancy-free transition metal doped BiOBr nanosheets;
(2) preparing an oxygen-vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst by a secondary solvothermal method:
ultrasonically dispersing the oxygen vacancy-free transition metal doped BiOBr nanosheet prepared in the step (1) into ethylene glycol, stirring for 1h, then placing the mixture into a stainless steel autoclave, keeping the stainless steel autoclave at 433K for 12h, cooling to room temperature, collecting precipitate, washing and drying to obtain an oxygen vacancy-free transition metal doped BiOBr nanosheet photocatalyst; the oxygen-vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst takes water as a solvent and visible light as a driving force to catalyze nitrogen to reduce to generate ammonia;
the transition metal salt in the step (1) is one of ferric chloride, ammonium molybdate and nickel chloride dihydrate.
2. The oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst of claim 1, wherein: in the step (1), the concentration of bismuth nitrate in the nitric acid solution containing bismuth nitrate is 48.5 g/L, and the concentration of nitric acid is 63 g/L; the concentration of the potassium bromide is 23.8 g/L; the concentration of the transition metal salt is 0.08M; the volume ratio of the potassium bromide solution to the nitric acid solution containing bismuth nitrate is 1: 2.
3. The oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst of claim 1, wherein: the molar ratio of the transition metal salt to the bismuth nitrate in the step (1) is 0.5-3%.
4. The oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst of claim 1, wherein: the concentration of the transition metal-doped BiOBr nanosheet free of oxygen vacancies in the step (2) and the concentration of the transition metal-doped BiOBr nanosheet free of oxygen vacancies in the ethylene glycol mixed solution are 19 g/L.
5. The oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst of claim 1, wherein: the wavelength of the visible light is greater than 400 nm.
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| CN109331846A (en) * | 2018-11-14 | 2019-02-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the compound bismuth tungstate of nano silver/silver bromide and products thereof and application |
| CN109759122A (en) * | 2019-03-19 | 2019-05-17 | 辽宁大学 | A kind of bismuth oxybromide ternary heterojunction structure photochemical catalyst and its preparation method and application |
| CN110079816A (en) * | 2019-04-30 | 2019-08-02 | 太原师范学院 | A kind of device and method of photoelectrocatalysis fixed nitrogen synthesis ammonia |
-
2019
- 2019-12-31 CN CN201911418887.5A patent/CN111036243B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331846A (en) * | 2018-11-14 | 2019-02-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the compound bismuth tungstate of nano silver/silver bromide and products thereof and application |
| CN109759122A (en) * | 2019-03-19 | 2019-05-17 | 辽宁大学 | A kind of bismuth oxybromide ternary heterojunction structure photochemical catalyst and its preparation method and application |
| CN110079816A (en) * | 2019-04-30 | 2019-08-02 | 太原师范学院 | A kind of device and method of photoelectrocatalysis fixed nitrogen synthesis ammonia |
Non-Patent Citations (2)
| Title |
|---|
| "Efficient Visible Light NitrogenFixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets"，;Hao Li et al.,;《J.Am.Chem.Soc.》;20150415;第137卷;6393-6399 * |
| "不同溴源制备铁掺杂BiOBr及其可见光光催化活性研究";李新玉等;《分子催化》;20131231;第27卷(第6期);575-584 * |
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