CN113398944B - Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof - Google Patents
Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 58
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 58
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 31
- 239000011029 spinel Substances 0.000 title claims abstract description 31
- 150000002815 nickel Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910052963 cobaltite Inorganic materials 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 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 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 229910002915 BiVO4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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—
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention belongs to the technical field of nano composite materials, and particularly relates to a composite material of bismuth vanadate surface modified nickel cobaltite and preparation and application thereof, wherein the preparation method of the composite material of bismuth vanadate surface modified nickel cobaltite comprises the following steps of S1: adding bismuth nitrate and ammonium metavanadate into an acid solution, adjusting the pH value to 0.25-2, and heating for reaction to obtain decahedral bismuth vanadate; s2: dispersing the decahedral bismuth vanadate obtained in S1 in a solvent, adding a nickel cobaltate precursor, heating for reaction, centrifugally drying the obtained product, and calcining. The composite material of bismuth vanadate surface modified nickel cobaltate spinel is a novel composite material with controllable structure, high visible light absorption efficiency, excellent performance and good stability, and has excellent performance on photocatalytic water oxidation; the raw materials used in the preparation method are low in cost, easy to obtain, simple and convenient in experimental operation, and expensive equipment is not used in the whole process, so that the method is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a bismuth vanadate surface modified nickel cobaltite composite material, and preparation and application thereof.
Background
Energy is an important guarantee for promoting social development and scientific and technical progress, people are facing to the increasingly serious problem of energy shortage along with economic development and rapid industrialization, and solar-driven photocatalytic water-splitting hydrogen production has great potential in solving the aspect of energy sustainability development. The water decomposition comprises two parts of water oxidation and reduction, wherein, the kinetic barrier can be overcome only by four electron transfer in the water oxidation reaction, and the water decomposition is the speed-determining step of the photocatalytic water decomposition, so that the design of the high-activity photocatalytic material for promoting the water oxidation becomes the key point of attention of people.
As a visible light response semiconductor photocatalyst, bismuth-based catalytic materials (bismuth vanadate) have the advantages of wider band gap (2.4eV), better stability, easiness in preparation and the like, and are widely researched, however, the bismuth-based catalytic materials still have the defect of rapid recombination of photo-generated electron-hole pairs, and further limit the application.
The recombination of electron-hole can be effectively inhibited by constructing the heterojunction, the nickel cobaltate spinel material has rich reserves and simple preparation method, and two metal redox couples of Co exist2+/Co3+And Ni2+/Ni3+The modified catalyst can be used as a cocatalyst to form heterojunction to inhibit the recombination of electron-hole pairs, and can provide abundant redox active sites for reaction to improve the photocatalytic performance. In the prior literature reports, nickel cobaltate spinel materials are frequently used in the electrochemical field and have limited application in the photochemical field.
Disclosure of Invention
The invention aims to solve the problems and provides a bismuth vanadate surface modified nickel cobaltite composite material, and preparation and application thereof, which can effectively inhibit electron-hole recombination of bismuth-based catalytic materials and can be widely applied to the field of photocatalytic water oxidation.
According to the technical scheme of the invention, the preparation method of the composite material of bismuth vanadate surface modified nickel cobaltate spinel comprises the following steps,
s1: adding bismuth nitrate and ammonium metavanadate into an acid solution, adjusting the pH value to 0.25-2, and heating for reaction to obtain decahedral bismuth vanadate;
s2: dispersing the decahedral bismuth vanadate obtained in the step S1 in a solvent, adding a nickel cobaltate precursor, heating for reaction, centrifugally drying the obtained product, and calcining to obtain the bismuth vanadate/nickel cobaltate spinel composite material, namely the bismuth vanadate surface modified nickel cobaltate spinel composite material.
Further, in the step S1, the mass ratio of bismuth nitrate to ammonium metavanadate is 7-14: 2-5, preferably, the mass ratio is 7: 2.
further, the acidic solution in the step S1 is a nitric acid solution, specifically, dilute nitric acid with a concentration of 2-5 mol/L. When the mass of the bismuth nitrate is 2.45g and the concentration of the nitric acid solution is 2mol/L, the volume of the bismuth nitrate and the dilute nitric acid is 20-40 mL, and the volume of the bismuth nitrate and the dilute nitric acid is preferably 35 mL.
Further, the adjustment of the pH value in step S1 is realized by adding ammonia, ammonium bicarbonate or sodium carbonate.
Specifically, the mass fraction of the ammonia water is 25 wt%, the adding amount is 2-10 ml, preferably 6ml, and the adding mode is dropwise adding.
Further, the product obtained after the heating reaction in the step S1 is washed with water and ethanol, and then dried in an oven.
Further, the solvent in the step S2 is water and ethanol with a volume ratio of 1-3: 5 to 10 parts of a mixed solvent.
Further, the nickel cobaltate precursor in the step S2 includes a nickel salt, a cobalt salt, a surfactant and a precipitating agent.
Further, the nickel salt is nickel nitrate or nickel chloride, the cobalt salt is cobalt nitrate or cobalt chloride, the surfactant is PVP (polyvinylpyrrolidone) or CTAB (cetyltrimethylammonium bromide), and the precipitator is urea; the mass ratio of the nickel salt to the cobalt salt to the surfactant to the precipitant is (5-8): 10-12: 80-120: 80-120 parts.
Further, the heating reaction in the step S1 is carried out at the temperature of 150-200 ℃ for 18-36 h; the heating reaction in the step S2 is carried out at the temperature of 60-100 ℃ for 8-12 h; the calcining temperature is 200-400 ℃, the time is 2-4 h, and the heating rate is 2-10 ℃/min.
Preferably, the heating reaction in the step S1 is carried out at 200 ℃ for 24 h; the heating reaction in the step S2 is carried out at the temperature of 90 ℃ for 8 h; the calcining temperature is 300 ℃, the time is 3h, and the heating rate is 5 ℃/min.
Further, in the step S2, after the nickel cobaltate precursor is added, the mixture is stirred at room temperature for 20 to 40 minutes.
Further, in the step S2, the drying temperature is 80 ℃.
Specifically, the preparation method of the composite material of bismuth vanadate surface modified nickel cobaltite comprises the following steps,
s1: adding 2.45-3.2 g of bismuth nitrate and 0.7-1.4 g of ammonium metavanadate into 20-40 mL of 2mol/L dilute nitric acid solution, adjusting the pH value to 0.25-2 by using 25 wt% ammonia water, transferring into a hydrothermal reaction kettle, reacting for 18-36 h at 150-200 ℃ to obtain decahedral bismuth vanadate, and drying in an oven;
s2: dispersing the decahedral bismuth vanadate obtained from S1 in water and ethanol at a volume ratio of 1: 7, adding the mixture into a solvent mixture with the mass ratio of 5: 10: 80: 80, stirring the mixture for 20-40 min at room temperature; then reacting for 8-12 h at 60-100 ℃, and centrifugally drying the obtained product at 80 ℃; and (3) calcining the dried sample in a tubular furnace at the calcining temperature of 200-400 ℃ for 2-4 h at the heating rate of 2-10 ℃/min to obtain the bismuth vanadate/nickel cobaltate spinel composite material, namely the bismuth vanadate surface modified nickel cobaltate spinel composite material.
The second aspect of the invention provides a bismuth vanadate surface modified nickel cobaltite composite material prepared by any one of the preparation methods.
The third aspect of the invention provides an application of the composite material of bismuth vanadate surface modified nickel cobaltate spinel for photocatalytic water oxidation.
The decahedral bismuth vanadate material is prepared by taking bismuth nitrate and ammonium metavanadate as precursors and water and nitric acid as solvents through a simple hydrothermal method, and has the advantages of controllable structure, good repeatability and easiness in preparation. And then the composite material of nickel cobaltate spinel and bismuth vanadate is synthesized by heating the composite material by taking the composite material as a carrier material and cobalt nitrate, nickel nitrate, urea and polyvinylpyrrolidone as precursors, wherein the cobalt nitrate and the nickel nitrate are taken as a cobalt source and a nickel source, the urea adjusts the pH value of the solution to make the solution display alkalescence, and the polyvinylpyrrolidone is taken as a surfactant to control the growth direction of the nickel cobaltate material. After modification, recombination of photoproduction electron-hole is inhibited, and the photocatalysis performance is greatly improved.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the preparation method of the composite material for modifying the surface of the bismuth vanadate with the nickel cobaltate spinel has the advantages of low cost of raw materials, easy obtainment, simple and convenient experimental operation, no expensive equipment in the whole process, and contribution to industrial production;
2. the composite material for modifying the nickel cobaltate spinel on the surface of the bismuth vanadate is a novel composite material with controllable structure, high visible light absorption efficiency, excellent performance and good stability, has excellent performance on photocatalytic water oxidation, can be used for supplying oxygen in water in a fish tank and the like, and is very beneficial to industrial application.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of bismuth vanadate according to example;
FIG. 2 is a Scanning Electron Micrograph (SEM) of bismuth vanadate according to the example;
FIG. 3 is a Transmission Electron Micrograph (TEM) of a bismuth vanadate/nickel cobaltite spinel (BVO/NCO) composite of an example;
FIG. 4 is a Scanning Electron Micrograph (SEM) of a bismuth vanadate/nickel cobaltite spinel (BVO/NCO) composite according to an example;
FIG. 5 is a graph showing the effect of photocatalytic water oxidation of a bismuth vanadate/nickel cobaltate spinel (BVO/NCO) composite material according to an example.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example one
(1) Decahedral bismuth vanadate (BiVO)4) The preparation method comprises the following specific steps:
adding 2.45g of bismuth nitrate and 0.7g of ammonium metavanadate into 35ml of 2mol/L dilute nitric acid, stirring vigorously at room temperature, then dropwise adding 6ml of 25 wt% ammonia water into the mixed solution, stirring until the solution becomes light yellow (the pH value is 0.25-2), and then transferring the solution into a reaction kettleReacting for 18-36 h at 150-200 ℃, then washing the reaction product with water, and drying in a drying oven to obtain BiVO4. The obtained BiVO4The TEM image of the crystal is shown in FIG. 1, and the SEM image is shown in FIG. 2, from which it can be seen that decahedral bismuth vanadate was successfully prepared and had a uniform size.
(2) The preparation method of the bismuth vanadate/nickel cobaltite spinel (BVO/NCO) composite material comprises the following specific steps:
dispersing 50mg of the prepared bismuth vanadate into a mixed solution containing 10ml of water and 70ml of ethanol, then adding 12.5mg of nickel nitrate, 25mg of cobalt nitrate, 200mg of urea and 200mg of polyvinylpyrrolidone into the mixed solution, and stirring for 20-40 minutes at room temperature; after the reaction is finished, carrying out heating reaction for 8-12 h at the temperature of 60-100 ℃; and centrifuging and drying the product, calcining the dried sample in a tubular furnace at 200-400 ℃ for 2-4 h in the air atmosphere, and raising the temperature at 2-10 ℃/min to finally obtain the BVO/NCO composite material.
The TEM image and the SEM image of the BVO/NCO composite material are respectively shown in FIG. 3 and FIG. 4, and it can be seen that the nickel cobaltate spinel is in a sheet structure and is successfully modified on the surface of the bismuth vanadate.
Test embodiment one
The photocatalytic water oxidation performance test under the visible light condition comprises the following specific steps:
the photocatalytic oxygen evolution activity of the BVO/NCO composite material obtained in the first example was evaluated by LabSolar-6A (Pofely, Beijing) photocatalytic on-line system. 50mg of the BVO/NCO photocatalyst obtained in example one are dispersed in 100ml of a solution containing 85mg of AgNO3And 200mg of La2O3The ultra pure water of (1) was dispersed by ultrasonic wave, then transferred to a reactor and sealed, then the reactor was degassed to remove air in the system, 5ml of nitrogen gas was injected into the reactor after the end, a performance test was performed using a 300W xenon lamp as simulated sunlight, and O was analyzed by an on-line gas chromatograph with TCD detector (GC D7900P)2Production rate (every 0.5 hours). And (4) preparing an oxygen standard curve after the test is finished, and obtaining the oxygen yield of the BVO/NCO photocatalyst according to the standard curve. FIG. 5 shows an embodiment BAnd the VO/NCO composite material has the effect of photocatalytic water oxidation. As shown in the attached figure 5, the BVO/NCO composite material has excellent photocatalytic water oxidation performance, wherein the optimal catalyst oxygen production efficiency can reach 1602 mu mol/h.g.
Example two
(1) Decahedral bismuth vanadate (BiVO)4) The preparation method comprises the following specific steps:
adding 2.9g of bismuth nitrate and 1.1g of ammonium metavanadate into 20ml of 5mol/L dilute nitric acid, stirring vigorously at room temperature, then dropwise adding an ammonium bicarbonate solution into the mixed solution, stirring until the solution becomes light yellow (the pH value is 0.25-2), then transferring the solution into a reaction kettle, reacting for 18-36 h at 150-200 ℃, then washing the reaction product with water, and placing the reaction product into an oven for drying to obtain BiVO4。
(2) The preparation method of the bismuth vanadate/nickel cobaltite spinel (BVO/NCO) composite material comprises the following specific steps:
dispersing 50mg of the prepared bismuth vanadate into a mixed solution containing 30ml of water and 50ml of ethanol, then adding 12.5mg of nickel chloride, 30mg of cobalt chloride, 240mg of urea and 240mg of hexadecyl trimethyl ammonium bromide into the mixed solution, and stirring for 20-40 minutes at room temperature; after the reaction is finished, carrying out heating reaction for 8-12 h at the temperature of 60-100 ℃; and centrifuging and drying the product, calcining the dried sample in a tubular furnace at 200-400 ℃ for 2-4 h in the air atmosphere, and raising the temperature at 2-10 ℃/min to finally obtain the BVO/NCO composite material.
EXAMPLE III
(1) Decahedral bismuth vanadate (BiVO)4) The preparation method comprises the following specific steps:
adding 3.2g of bismuth nitrate and 1.4g of ammonium metavanadate into 40ml of 3.5mol/L dilute nitric acid, stirring vigorously at room temperature, then dropwise adding a sodium carbonate solution into the mixed solution, stirring until the solution becomes light yellow (the pH value is 0.25-2), then transferring the solution into a reaction kettle, reacting for 18-36 h at 150-200 ℃, then washing the reaction product with water, and placing the reaction product into an oven for drying to obtain BiVO4。
(2) The preparation method of the bismuth vanadate/nickel cobaltite spinel (BVO/NCO) composite material comprises the following specific steps:
dispersing 50mg of the prepared bismuth vanadate into a mixed solution containing 20ml of water and 100ml of ethanol, then adding 20mg of nickel nitrate, 28mg of cobalt nitrate, 300mg of urea and 300mg of polyvinylpyrrolidone into the mixed solution, and stirring for 20-40 minutes at room temperature; after the reaction is finished, carrying out heating reaction for 8-12 h at the temperature of 60-100 ℃; and centrifuging and drying the product, calcining the dried sample in a tubular furnace at 200-400 ℃ for 2-4 h in the air atmosphere, and raising the temperature at 2-10 ℃/min to finally obtain the BVO/NCO composite material.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
1. A preparation method of a composite material of bismuth vanadate surface modified nickel cobaltite is characterized by comprising the following steps,
s1: adding bismuth nitrate and ammonium metavanadate into an acid solution, adjusting the pH value to 0.25-2, and heating for reaction to obtain decahedral bismuth vanadate;
s2: dispersing the decahedral bismuth vanadate obtained in the step S1 in a solvent, adding a nickel cobaltate precursor, heating for reaction, centrifugally drying the obtained product, and calcining to obtain a bismuth vanadate/nickel cobaltate spinel composite material, namely the composite material of bismuth vanadate surface modified nickel cobaltate spinel;
the nickel cobaltate precursor comprises nickel salt, cobalt salt, a surfactant and a precipitator, wherein the surfactant is PVP or CTAB.
2. The method for preparing the bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 1, wherein the mass ratio of bismuth nitrate to ammonium metavanadate in the step S1 is 7-14: 2 to 5.
3. The method for preparing a bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 1, wherein the acidic solution in the step S1 is a nitric acid solution.
4. The method for preparing a bismuth vanadate surface modified nickel cobaltate spinel composite material according to claim 1, wherein the pH value is adjusted in the step S1 by adding ammonia water, ammonium bicarbonate or sodium carbonate.
5. The method for preparing the bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 1, wherein the solvent in the step S2 is water and ethanol in a volume ratio of 1-3: 5 to 10 parts of a mixed solvent.
6. The method for preparing a bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 1, wherein the nickel salt is nickel nitrate or nickel chloride, the cobalt salt is cobalt nitrate or cobalt chloride, and the precipitant is urea; the mass ratio of the nickel salt to the cobalt salt to the surfactant to the precipitant is (5-8): 10-12: 80-120: 80-120 parts.
7. The method for preparing the bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 1, wherein the heating reaction temperature in the step S1 is 150-200 ℃, the heating reaction temperature in the step S2 is 60-100 ℃, and the calcining temperature is 200-400 ℃.
8. The composite material of bismuth vanadate surface modified nickel cobaltite spinel prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the bismuth vanadate surface modified nickel cobaltite spinel composite material according to claim 8 for photocatalytic water oxidation.
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