CN111229240B - Bismuth ferrite catalyst and preparation method and application thereof - Google Patents
Bismuth ferrite catalyst and preparation method and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 114
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000012670 alkaline solution Substances 0.000 claims abstract description 20
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 19
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 19
- 239000000661 sodium alginate Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 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 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002897 Bi2Fe4O9 Inorganic materials 0.000 description 1
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
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- A—HUMAN NECESSITIES
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- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a bismuth ferrite catalyst and a preparation method and application thereof. The preparation method comprises the steps of preparing a bismuth ferrite precursor by taking a sodium alginate aqueous solution as a crystal growth guiding agent, mixing the bismuth ferrite precursor with an alkaline solution, and reacting at a temperature suitable for the reaction of the bismuth ferrite precursor with the alkaline solution to obtain the bismuth ferrite catalyst. The bismuth ferrite catalyst is a pure-phase catalyst, has the characteristics of simple preparation method, high crystal crystallinity and regular crystal morphology, has obviously improved catalytic performance, and has wide application prospect in the aspects of photocatalytic hydrogen production and photocatalytic degradation of pollutants.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a bismuth ferrite catalyst, a preparation method and application thereof.
Background
Multiferroic materials refer to a class of intelligent materials that have two or more ferroic sequences (e.g., ferroelectric, magnetic, etc.) simultaneously, and have entered into the hot scientific problem published in the journal of the U.S. science, 2007. Bismuth ferrite Bi2Fe4O9(BFO) as room temperature single-phase multiferroic material not only has excellent ferroelectric property, but also can realize the control of magnetization by electric field due to the coupling effect among electricity, magnetism and strain, thus being a hotspot for researching novel multiferroic material. The catalyst material has an antiferromagnetic Narl temperature and a ferroelectric Curie temperature which are far higher than room temperature, and is one of a few single-phase multiferroic materials which simultaneously have ferroelectricity and parasitic weak ferromagnetism under the room temperature condition.
In the application field of photocatalysis, especially solar energy is used as a new energy source, and water can be decomposed into hydrogen and oxygen by using a photocatalyst. Since the decomposition of water to generate oxygen is a four-electron reaction, it is a rate-determining step of water decomposition, and thus it is necessary to develop a photocatalyst for high-efficiency decomposition of water to generate oxygen. At present, a large number of catalysts for photocatalytic decomposition of water to produce oxygen, including titanium oxide, bismuth vanadate, tungsten oxide, etc., have been developed in an effort to prepare high-efficiency semiconductor-based photocatalysts. The bismuth ferrite is used as an n-type semiconductor, has low raw material cost, is nontoxic and harmless, and is used for photocatalytic water decomposition, environmental pollutant treatment and the like. And due to the proper narrow band gap (about 2.0eV) and the relatively positive valence band position (about 2.5V), the demand of photocatalytic water decomposition for oxygen production can be met thermodynamically. These particular properties have great application potential and commercial prospects.
At present, various preparation methods are used for preparing bismuth ferrite materials, such as a solid-phase sintering method, a magnetron sputtering method, a rapid liquid-phase sintering method, a sol-gel method, a hydrothermal method, a microwave hydrothermal method and the like. The traditional preparation method usually needs presintering at 600 ℃ and then heating to 750-850 ℃ to obtain the product. In addition, the bismuth ferrite particles obtained by the traditional preparation method are large and difficult to adjust in size. Although researches show that the temperature can be reduced by adding the organic auxiliary agent, the cost is higher, and the industrial production is not facilitated.
For example, CN101890354A discloses a preparation method of bismuth ferrite photocatalyst for degrading organic pollutants in water. The method adopts a solvothermal method to synthesize the photocatalyst bismuth ferrite, and the molar ratio of bismuth nitrate to ferric nitrate is 12: 1, adopting a xenon lamp as a light source, and then fully mixing bismuth ferrite with neutral red solutions with different concentrations to carry out photocatalytic degradation on neutral red dyes in the aqueous solution. However, the catalyst synthesized by the method has large particle size, so the reaction specific surface area is smaller.
For another example, Wangben prepares nano-scale bismuth ferrite powder by combining an ultrasonic chemical method and a self-propagating method. However, the X-ray diffraction (XRD) data show that the prepared powder is nano-scale bismuth ferrite containing a small amount of impure phase. The prepared powder is analyzed by a transmission electron microscope and a particle size analyzer, and the radius of the nano particles can be effectively reduced by ultrasonic wave [ Wangben, synthesis and modification of multiferroic bismuth ferrite [ D ]. Suzhou university, 2013 ].
Therefore, finding a new method with simple preparation method and adjustable bismuth ferrite particle size is a challenge in bismuth ferrite catalyst synthesis. In addition, the charge mobility and the photogenerated charge recombination of the bismuth ferrite catalyst are far from reaching the ideal level, and further improvement is still needed.
Disclosure of Invention
In order to solve at least part of technical problems in the prior art, the inventor carries out intensive research, and finds that a bismuth ferrite precursor is prepared by adding a sodium alginate aqueous solution as a crystal growth guiding agent, and a bismuth ferrite pure-phase catalyst with adjustable particle size and a nanoscale sheet structure can be prepared by controlling the concentration and the reaction time of an alkaline solution, so that the catalytic performance of the catalyst is greatly improved. The present invention has been accomplished based at least in part on this finding. Specifically, the present invention includes the following.
In a first aspect of the present invention, a method for preparing a bismuth ferrite catalyst is provided, which comprises the following steps:
(1) the preparation method of the bismuth ferrite precursor comprises the steps of mixing an iron source and a sodium alginate aqueous solution, adding a bismuth source, and uniformly stirring to obtain the bismuth ferrite precursor; and
(2) and a step of preparing the bismuth ferrite catalyst, which comprises mixing the bismuth ferrite precursor with an alkaline solution, and carrying out mixing reaction at a temperature suitable for the reaction of the bismuth ferrite precursor with the alkaline solution to obtain the bismuth ferrite catalyst.
Preferably, in the method for preparing a bismuth ferrite catalyst according to the present invention, the iron source is at least one selected from the group consisting of iron oxide, iron nitrate, iron chloride and iron sulfate, and the bismuth source is at least one selected from the group consisting of bismuth chloride, bismuth nitrate and bismuth oxide.
Preferably, in the preparation method of the bismuth ferrite catalyst, the concentration of the sodium alginate aqueous solution is 3-30 mg/mL.
Preferably, in the preparation method of the bismuth ferrite catalyst according to the present invention, the molar ratio of the iron source to the bismuth source in the step (1) is 1 to 4: 0.2-3.
Preferably, in the method for preparing a bismuth ferrite catalyst according to the present invention, the temperature of the step (2) is 180-300 ℃.
Preferably, in the method for preparing a bismuth ferrite catalyst according to the present invention, the volume ratio of the bismuth ferrite precursor to the alkaline solution in the step (2) is 1:1, and the concentration of the alkaline solution is 2 to 9mol/L, and the solution is selected from an aqueous solution of sodium hydroxide or potassium hydroxide.
Preferably, the method for preparing a bismuth ferrite catalyst according to the present invention further comprises a washing step comprising contacting the bismuth ferrite catalyst obtained in step (2) with deionized water and washing.
In a second aspect of the present invention, there is provided a bismuth ferrite catalyst obtained by the production method according to the first aspect.
Preferably, the bismuth ferrite catalyst according to the present invention has a micro-scale plate-like structure, and the length of the micro-scale plate-like structure is 2 to 5 micrometers.
In a third aspect of the invention, there is provided the use of a bismuth ferrite catalyst in photocatalysis.
Preferably, the bismuth ferrite catalyst provided by the invention is used in photocatalysis, and the use comprises photocatalytic hydrogen production from water and treatment of environmental pollutants.
The bismuth ferrite catalyst prepared by the preparation method is a pure-phase catalyst, and compared with the conventional catalyst and the preparation method thereof, the bismuth ferrite catalyst has the characteristics of simple preparation method, high crystal crystallinity and regular crystal morphology, and the catalytic performance is obviously improved. In the field of catalysts, particularly relates to photocatalytic hydrogen production and photocatalytic degradation of pollutants, and has wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction chart of a bismuth ferrite catalyst prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the bismuth ferrite catalyst prepared in example 1 of the present invention.
FIG. 3 is an exemplary bismuth ferrite catalyst of the present inventionPhotocurrent performance plots of the agents. As shown, the photocurrent density without sodium alginate addition was about 10. mu.A/cm2Secondly, the photocurrent density of bismuth ferrite prepared by adding sodium alginate is 40 muA/cm2The increase is four times, which indicates that the separation efficiency of photo-generated electrons and holes is increased.
FIG. 4 is a graph of the photocatalytic degradation of methylene blue by an exemplary bismuth ferrite catalyst of the present invention. As shown in figure 4, the degradation rate of bismuth ferrite prepared by adding sodium alginate can reach 100% within 50 min.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.
[ preparation method of bismuth ferrite catalyst ]
The first aspect of the invention provides a preparation method of a bismuth ferrite catalyst, which comprises the following steps:
(1) the preparation method of the bismuth ferrite precursor comprises the steps of mixing an iron source and a sodium alginate aqueous solution, adding a bismuth source, and uniformly stirring to obtain the bismuth ferrite precursor; and
(2) and a step of preparing the bismuth ferrite catalyst, which comprises mixing the bismuth ferrite precursor with an alkaline solution, and carrying out mixing reaction at a temperature suitable for the reaction of the bismuth ferrite precursor with the alkaline solution to obtain the bismuth ferrite catalyst.
The step (1) is a preparation process of the bismuth ferrite catalyst precursor. Wherein the iron source provides iron elements of the bismuth ferrite precursor, and the bismuth source provides bismuth elements of the bismuth ferrite precursor. Preferably, the iron source is at least one selected from the group consisting of iron oxide, iron nitrate, iron chloride and iron sulfate. In a particular embodiment, the iron source is ferric chloride. Preferably, the bismuth source is at least one selected from the group consisting of bismuth chloride, bismuth nitrate and bismuth oxide. In a specific embodiment, the bismuth source is bismuth nitrate.
Preferably, the molar ratio of the iron source to the bismuth source is 1-4: 0.2-3. More preferably, the molar ratio of the iron source to the bismuth source is 2-4:1, still more preferably 2: 1.
The sodium alginate mixed with the iron source in the step (1) is used as a guiding agent for the growth of the bismuth ferrite crystal in the invention. The inventor finds out through a large number of experiments that the concentration of sodium alginate and the proportion of sodium alginate in a preparation system are one of the influencing factors for forming the pure-phase bismuth ferrite catalyst with the nano-flake structure. In the invention, carboxyl and hydroxyl in the active site of sodium alginate have lone pair electrons, and have chelation with iron ions in the invention to guide the ordered growth of crystals. Meanwhile, the length of the nano structure is controlled by controlling the specific ratio of the iron source and the bismuth source. Preferably, the concentration of the sodium alginate aqueous solution is 3-30 mg/mL. More preferably, the concentration of the sodium alginate aqueous solution is 5-28 mg/mL. Also preferably 5-25 mg/mL.
And (2) mixing and reacting the alkaline solution at a temperature suitable for the reaction of the bismuth ferrite precursor and the alkaline solution to obtain pure-phase bismuth ferrite with a sheet shape. The inventor finds that the alkaline solution with a certain concentration has excellent effect and is more beneficial to forming a crystal form with a sheet structure. The alkaline solution may be a strong alkali type aqueous solution or a weak alkali type aqueous solution, such as an aqueous ammonia solution. The alkaline solution of the present invention is preferably a strong alkaline solution. Also preferably, the strong alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
Preferably, the volume ratio of the bismuth ferrite precursor to the strong alkali solution in step (2) of the invention is 1:1, and the concentration of the strong alkali solution is 2-9mol/L, and preferably 4-7 mol/L. The temperature at which the reaction is carried out after mixing is preferably 180-300 ℃ and more preferably 180-200 ℃. In a specific embodiment, the reaction temperature is 200 ℃. The reaction time is preferably 12 to 30 hours, and more preferably 12 to 24 hours. The apparatus for carrying out the reaction can be carried out in a known manner, for example by means of a stainless steel reactor.
[ washing step ]
The preparation method of the present invention optionally further comprises a washing step. Which comprises contacting the bismuth ferrite catalyst obtained in step (2) with deionized water and washing it, whereby the purity of the catalyst can be improved, in particular impurities which are not removed in the synthesis process are removed. Such impurities include, but are not limited to, inorganic salts such as sodium and/or potassium salts, which are dried to obtain the bismuth ferrite catalyst. The washing may be carried out once or a plurality of times, for example, two or three times. The conditions for the drying process after washing are at atmospheric pressure. The drying temperature is not particularly limited, and may be carried out at room temperature.
It will be understood by those skilled in the art that other steps or operations, such as further optimization and/or improvement of the method of the present invention, may be included before, after, or between steps (1) and (2) as long as the objectives of the present invention are achieved.
The inventor finds that the pure-phase bismuth ferrite catalyst with ideal catalytic performance can be obtained by taking sodium alginate as a crystal growth guiding agent, controlling the proportion of an iron source and a bismuth source and controlling the alkaline condition in the synthesis process. In addition, in conventional synthesis, the problem of impurity phase doping tends to occur due to the crystallization process, especially for example, BiFeO3、α-Fe2O3、β-Bi2O3And unstable Bi25FeO40The intermediate has a problem of impurity phase, and the segregation phenomenon in the crystallization process can be avoided by the method of the invention. In addition, the bismuth ferrite particles and the size can be adjusted, so that the catalytic performance can be obviously improved, and the method has wide industrial application prospect.
[ bismuth ferrite catalyst ]
In a second aspect of the invention, a bismuth ferrite catalyst is provided, which is prepared by the method of the invention. Preferably, it has a lamellar structure of microns, and the length of the lamellar structure is 2-5 microns. The bismuth ferrite catalyst has a sheet structure capable of exposing more active sites, and a micron-sized structure solves the problems of low charge mobility and easy recombination of photo-generated charges of the traditional bismuth ferrite catalyst, obviously reduces the recombination probability of photo-generated electrons and holes, and obviously improves the photocatalytic performance. In addition, the bismuth ferrite catalyst has a special size effect, which is reflected in that when a space spiral modulation structure leads to the offset of ion magnetic moment, the size of the catalyst material is more and more emphasized on the research of catalytic performance.
[ use of bismuth ferrite catalyst ]
In a third aspect of the invention, the use of the bismuth ferrite catalyst in photocatalysis is provided, preferably, the use includes but is not limited to the use in photocatalytic water hydrogen production and environmental pollutant treatment.
Examples
This example is an exemplary method of preparing a bismuth ferrite catalyst comprising the steps of:
(1) preparing a bismuth ferrite precursor:
0.1g to 0.5g of sodium alginate is dissolved in 20mL of deionized water and fully and uniformly stirred. Adding 2-4mmol of ferric chloride (or ferric sulfate, ferric nitrate, etc.) into the sodium alginate solution, fully stirring, and adding 1-2mmol of bismuth nitrate to make the molar ratio of bismuth to iron 1: 2. Stirring evenly to obtain a brown precursor mixture.
(2) 20mL of 4-7mol/L NaOH aqueous solution was added dropwise to the precursor mixture. After being stirred evenly, the mixture is transferred into a 100mL stainless steel reaction kettle and is hydrothermally treated for 12 to 24 hours at the temperature of 200 ℃. And fully washing and drying the obtained powder to obtain the bismuth ferrite micron sheet.
The X-ray diffraction pattern of the bismuth ferrite catalyst is shown in figure 1, and the result proves that the prepared bismuth ferrite is pure phase and has no impurities according to the comparison with the standard card 25-0090. In addition, the peak intensity is higher and the half-peak width is smaller, which indicates that the crystallinity of the prepared bismuth ferrite is higher.
The scanning electron micrograph of the bismuth ferrite catalyst is shown in FIG. 2, which shows that the prepared bismuth ferrite sample has a sheet-like morphology with a thickness of about 0.5 μm and a length and width of about 2-5 μm.
And (3) testing photocurrent: and (3) grinding 20mg of the photocatalytic material and iodine uniformly, adding the mixture into a proper amount of acetone, and performing ultrasonic treatment for 5min to uniformly mix the mixture. And (2) immersing the ITO conductive glass into an acetone solution, placing platinum sheet electrodes in parallel, applying a constant potential of 50V between the two electrodes by using a constant potential instrument, depositing for 10min, drying at room temperature, and roasting at 300 ℃ for 2h to obtain the photoelectrode. The photocurrent was measured at CHI760E electrochemical workstation by using a three-electrode system, the working electrode was a self-made thin-film photoelectrode, the reference electrode was an Ag/AgCl electrode, the counter electrode was a platinum sheet electrode, and the electrolyte was 0.5M Na2SO4The solution was treated with a 300W xenon lamp as a simulated light source. The photocurrent test results are shown in fig. 3.
Testing photocatalytic degradation performance: a50 mg sample was dispersed in 100mL of methylene blue solution (50 mg/L). Vertical illumination was performed using a 300W xenon lamp light source. After a period of time, 5mL of the solution is taken for centrifugal separation, the supernatant is taken, the absorbance is measured by an ultraviolet-visible spectrophotometer, and the degradation rate is calculated. The photocatalytic degradation performance results are shown in fig. 4.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
Claims (5)
1. The preparation method of the bismuth ferrite catalyst is characterized by comprising the following steps of:
(1) mixing an iron source and a sodium alginate aqueous solution, adding a bismuth source, and uniformly stirring to obtain a brown bismuth ferrite precursor mixture, wherein the concentration of the sodium alginate aqueous solution is 3-30 mg/mL; the molar ratio of the iron source to the bismuth source is 1-4: 0.2-3; and
(2) the preparation method of the bismuth ferrite catalyst comprises the steps of mixing the bismuth ferrite precursor mixture with an alkaline solution, uniformly stirring, transferring into a stainless steel reaction kettle, carrying out hydrothermal treatment at 200 ℃ for 12-24 hours, fully washing the obtained powder, and drying to obtain the bismuth ferrite catalyst with the thickness of 0.5 mu m and the length and width of 2-5 mu m and in a sheet shape; the volume ratio of the bismuth ferrite precursor mixture to an alkaline solution is 0.5-1.5:1, the concentration of the alkaline solution is 2-9mol/L, and the alkaline solution is selected from an aqueous solution of sodium hydroxide and/or potassium hydroxide.
2. The method for producing a bismuth ferrite catalyst according to claim 1, wherein the iron source is at least one selected from the group consisting of iron nitrate, iron chloride and iron sulfate; the bismuth source is at least one selected from the group consisting of bismuth chloride and bismuth nitrate.
3. The method of producing a bismuth ferrite catalyst according to claim 1, further comprising a washing step which comprises contacting the bismuth ferrite catalyst obtained in the step (2) with water and washing.
4. A bismuth ferrite catalyst obtained by the production method according to any one of claims 1 to 3.
5. The use of the bismuth ferrite catalyst according to claim 4 in photocatalytic water hydrogen production and environmental pollutant treatment.
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