CN110237836B - Molybdenum modified zirconium dioxide material and preparation method and application thereof - Google Patents
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 34
- -1 Molybdenum modified zirconium dioxide Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OAQPVOXRGWEZQS-UHFFFAOYSA-N O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] OAQPVOXRGWEZQS-UHFFFAOYSA-N 0.000 claims description 5
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical group O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 10
- 238000002474 experimental method Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
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- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- LRVUGEZGBKPRRZ-UHFFFAOYSA-L oxygen(2-);zirconium(4+);dichloride Chemical compound [O-2].[Cl-].[Cl-].[Zr+4] LRVUGEZGBKPRRZ-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 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
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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Abstract
The invention discloses a molybdenum-modified zirconium dioxide material and a preparation method thereof. The molybdenum modified zirconium dioxide material is a zirconium dioxide crystal coexisting in a monoclinic phase and a tetragonal phase, and the material is used for reducing CO in photocatalysis2In an activity test experiment, the activity of the molybdenum modified zirconium dioxide is obviously improved compared with that of unmodified zirconium dioxide, wherein the yield of carbon monoxide is improved by 12 times to the maximum, so that the material can be applied to the field of photocatalysis to reduce carbon dioxide.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a molybdenum modified zirconium dioxide material as well as a preparation method and application thereof.
Background
The large amount of carbon dioxide emitted from the combustion of fossil fuels is a root cause of global climate change, thus creating many environmental problems. Therefore, capturing carbon dioxide and converting it into energy utilization has become a global research issue. Carbon dioxide is used as an important carbon source, and carbon dioxide is converted into carbon monoxide or other carbon-containing compounds, so that the research of the chemical industry and the environmental industry is focused. In recent years, photocatalytic technology has attracted the attention of many researchers because of its many advantages, and it is expected that photocatalytic technology will reduce carbon dioxide to carbon monoxide or other carbon-containing compounds. It is generally recognized that wide band gap semiconductors generally require higher energy to transition electrons in the valence band to the conduction band, and that zirconium dioxide is one such wide band gap semiconductor.
Jia Gua et al reported on Fuel (241(2019) 129-137) that a molybdenum-modified zirconia material was prepared by hydrothermal, calcination and then impregnation using zirconyl dichloride as a precursor. The preparation method is applied to the methanation reaction of sulfur-resistant carbon monoxide, has good sulfur-resistant effect, but the preparation process is completed by two steps. Ba' rbara Samaranch et al reported on Chemistry of Materials (Vol.18, No.6,2006) that the prepared molybdenum-modified tetragonal zirconia did not cause changes in the crystal structure of zirconia with changes in the amount of modification, but increased the surface area. In summary, the above preparation processes and application fields have characteristics, but the prior preparation process usually needs to add a surfactant or a calcination process, and the preparation process is complex.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of molybdenum modified zirconium dioxide, which has simple preparation process and can save preparation time cost and raw material cost.
The second purpose of the invention is to provide a molybdenum-modified zirconium dioxide material which has photocatalytic activity and can reduce carbon dioxide into carbon monoxide.
The invention also aims to provide the application of the molybdenum modified zirconium dioxide material.
The invention is realized by the following technical scheme:
a preparation method of molybdenum modified zirconium dioxide comprises the following steps:
1) weighing a molybdenum source to prepare a molybdenum source aqueous solution;
2) taking a molybdenum source water solution, adding a zirconium source into the molybdenum source water solution, and uniformly stirring to obtain a mixed solution;
3) reacting the mixed solution obtained in the step 2) at 170-250 ℃ for 6-24 hours, and naturally cooling to room temperature after the reaction is finished to leave a lower-layer precipitate;
4) and washing the precipitate to be neutral, and then drying to obtain the molybdenum modified zirconium dioxide material.
Further, the ratio of the mass of molybdenum atoms to the mass of zirconium dioxide is in the range of 0.1% to 5%.
Further, the drying temperature in the step 4) is 50-80 ℃, and the drying time is 5-24 hours.
Further, the molybdenum source is sodium molybdate dihydrate, ammonium paramolybdate tetrahydrate or molybdenum nitrate pentahydrate.
Further, the zirconium source is zirconium nitrate pentahydrate, zirconium oxychloride, zirconium tetrachloride or zirconyl nitrate.
Further, the washing in the step 4) is specifically washing with deionized water and absolute ethyl alcohol for several times.
The invention also discloses a molybdenum-modified zirconium dioxide material prepared by the preparation method of the molybdenum-modified zirconium dioxide, wherein the molybdenum-modified zirconium dioxide material is a crystal and has a monoclinic phase (m-ZrO)2) And tetragonal phase (t-ZrO)2) Two crystalline phases.
The invention also discloses application of the molybdenum modified zirconium dioxide material as a photocatalyst in the field of photocatalytic reduction of carbon dioxide.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of molybdenum modified zirconium dioxide, which comprises the steps of mixing a zirconium source and a molybdenum source, reacting at a certain temperature to synthesize a molybdenum modified zirconium dioxide material, adopting a simpler hydrothermal method, and realizing molybdenum modified zirconium dioxide without adding a surfactant or a calcining process. The synthesis process has the characteristics of mild conditions, simple and convenient operation and safety, and the preparation process is simple and can save the preparation time cost and the raw material cost.
Furthermore, the mass ratio of the molybdenum element to the zirconium dioxide is 0.1-5%, the activity of the molybdenum modified zirconium dioxide material is improved in the interval, and the activity is slowly reduced when the activity exceeds the range.
Furthermore, if the drying temperature is too low, the drying time is too long, and if the drying temperature is too high, the chemical valence state of the molybdenum element exposed in hot air may be changed, and the temperature is selected from 50 ℃ to 80 ℃ through experiments.
Further, the materials available for the molybdenum source and the zirconium source are varied, and the raw materials are readily available.
The invention also discloses a molybdenum modified zirconium dioxide material, which is a zirconium dioxide crystal coexisting with a monoclinic phase and a tetragonal phase, has photocatalytic activity and can reduce carbon dioxide into carbon monoxide. In addition, the material has the characteristics of no toxicity, high temperature resistance, acid and alkali corrosion resistance, and is a photocatalytic material with good stability.
The invention also discloses application of the molybdenum modified zirconium dioxide material in photocatalytic reduction of CO2In activity test experiments, the activity of the molybdenum-modified zirconium dioxide is significantly improved compared with that of unmodified zirconium dioxide, wherein the yield of carbon monoxide is improved by 12 times to the maximum. In addition, the ultraviolet-visible diffuse reflection absorption spectrogram shows that the response to ultraviolet light is improved after molybdenum modification, so that the material can be applied to the field of photocatalysis to reduce carbon dioxide.
Drawings
FIG. 1 is an XRD pattern of examples 1 to 5 of the present invention;
FIG. 2 is an activity diagram of various molybdenum contents for all examples 1-5 of the present invention;
FIG. 3 is a UV-VIS diffuse reflectance absorption spectrum of example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
A preparation method of molybdenum modified zirconium dioxide comprises the following steps:
1) 100mg of ammonium paramolybdate tetrahydrate is weighed and dissolved in 100mL of deionized water, and the solution is shaken up to obtain the ammonium paramolybdate tetrahydrate solution with the concentration of 1 mg/mL.
2) Adding 0.5g of zirconium nitrate pentahydrate into 50mL of polytetrafluoroethylene lining, adding 2.58mL of ammonium paramolybdate tetrahydrate solution, stirring for 30 minutes, fully dissolving the solid, uniformly mixing, then putting the lining into a reaction kettle, and reacting for 10 hours at 200 ℃.
3) After the reaction is finished, naturally cooling, and leaving a lower-layer precipitate.
4) And washing the precipitate for several times by using deionized water and absolute ethyl alcohol until the pH value is 7, drying in an oven at 60 ℃ for 6 hours, and grinding to obtain the 1% molybdenum modified zirconium dioxide photocatalytic material (1% is the ratio of the mass of the molybdenum element to the mass of theoretical zirconium dioxide).
100mg of the sample obtained in example 1 was subjected to the ultraviolet-visible diffuse reflection test to obtain a graph shown in FIG. 3. As seen from FIG. 3, when the wavelength is less than 420nm, the absorption intensity of the modified material to ultraviolet light is obviously improved.
The semiconductor photocatalytic material has a band gap, valence band electrons can jump to a conduction band under illumination, the electrons have reducibility, and the electrons after the jump can react with CO adsorbed on the surface of the material2A reduction reaction occurs to produce CO. Thus, the response to ultraviolet light is improved, and the yield of CO can be improved. However, too much doping amount of molybdenum is not favorable for yield improvement, although photo response is improved since the active sites are covered with molybdenum. The activity was best when the molybdenum modification was 1%.
Example 2
A preparation method of molybdenum modified zirconium dioxide comprises the following steps:
1) 100mg of sodium molybdate dihydrate is weighed and dissolved in 100mL of deionized water, and the solution is shaken up to obtain the sodium molybdate dihydrate solution with the concentration of 1 mg/mL.
2) Adding 0.5g of zirconium oxychloride into 50mL of polytetrafluoroethylene lining, adding 2.363mL of sodium molybdate dihydrate solution, stirring for 30 minutes until the solid is fully dissolved, uniformly mixing, then putting the lining into a reaction kettle, and reacting for 6 hours at 250 ℃.
3) After the reaction is finished and the reaction product is naturally cooled, a lower precipitate is left.
4) And washing the precipitate with deionized water and absolute ethyl alcohol for several times until the pH value is 7, drying at 60 ℃ for 6 hours, and grinding to obtain the 0.5% molybdenum modified zirconium dioxide photocatalytic material (0.5% is the ratio of the mass of the molybdenum element to the mass of theoretical zirconium dioxide).
Example 3
A preparation method of molybdenum modified zirconium dioxide comprises the following steps:
1) weighing 100mg of molybdenum nitrate pentahydrate, dissolving in 100mL of deionized water, and shaking up to obtain a molybdenum nitrate pentahydrate solution with the concentration of 1 mg/mL.
2) Adding 0.5g of zirconyl nitrate into 50mL of polytetrafluoroethylene lining, adding 1.203mL of molybdenum nitrate pentahydrate solution, stirring for 30 minutes until the solid is fully dissolved, uniformly mixing, then putting the lining into a reaction kettle, and reacting for 10 hours at 180 ℃.
3) After the reaction is finished and the reaction product is naturally cooled, a lower precipitate is left.
4) And washing the precipitate with deionized water and absolute ethyl alcohol for several times until the pH value is 7, drying the precipitate for 6 hours at the temperature of 60 ℃, and then grinding the precipitate to obtain the 0.1 percent molybdenum modified zirconium dioxide photocatalytic material (0.1 percent is the ratio of the mass of the molybdenum element to the mass of theoretical zirconium dioxide).
Example 4
A preparation method of molybdenum modified zirconium dioxide comprises the following steps:
1) 100mg of ammonium paramolybdate tetrahydrate is weighed and dissolved in 100mL of deionized water, and the solution is shaken up to obtain a 1mg/mL ammonium paramolybdate tetrahydrate solution.
2) Adding 0.5g of zirconium tetrachloride into a 50mL polytetrafluoroethylene lining, adding 23.800mL of ammonium paramolybdate tetrahydrate solution, stirring for 30 minutes until the solid is fully dissolved, uniformly mixing, then placing the lining into a reaction kettle, and reacting for 24 hours at 170 ℃.
3) After the reaction is finished and the reaction product is naturally cooled, a lower precipitate is left.
4) And washing the precipitate for several times by using deionized water and absolute ethyl alcohol until the pH value is 7, drying for 6 hours at 60 ℃, and grinding to obtain the 5% molybdenum modified zirconium dioxide photocatalytic material (5% is the ratio of the mass of the molybdenum element to the mass of theoretical zirconium dioxide).
The addition amounts of the zirconium source and the molybdenum source are determined according to the following method:
wherein, the mass of the zirconium source is self-regulated, such as 500mg, and other results are further calculated.
150mg of the sample obtained in examples 1 to 4 was sampled,by X-ray diffraction, the XRD diffractogram shown in figure 1 was obtained. The peaks in fig. 1 are sharp, typical of zirconium dioxide crystals, and have no XRD diffraction peaks associated with molybdenum due to the small amount of modification. As can be seen from comparison of the peak positions in FIG. 1 with the standard cards (PDF- #86-1449, PDF- #88-1007), a monoclinic phase (m-ZrO) is present2) And a tetragonal phase (t-ZrO)2) Two crystalline phases.
The activity test process comprises the following steps: the samples 20mg and 20mg of zirconium dioxide of examples 1-4 were weighed, five experiments were performed, the five samples were dispersed in a petri dish with a diameter of 55mm, the petri dish was placed in a vacuum reaction apparatus, 20mL of carbon dioxide gas was added into the vacuum reaction apparatus by a syringe, 20 μ L of deionized water was injected, the samples were illuminated for 5 hours, and the product concentration was measured by gas chromatography every hour, so that the curve shown in fig. 2 was obtained.
As can be seen from fig. 2, the reduction of carbon dioxide and the yield of carbon monoxide are significantly improved in the samples of examples 1 to 4 compared to unmodified zirconia, and example 1 is the most preferable and can be improved by 12 times at most.
The molybdenum element is used for modifying zirconium dioxide, so that the response to ultraviolet light can be improved, and the yield of carbon monoxide can be increased, therefore, the molybdenum element can replace noble metals to achieve the purpose of increasing the yield of carbon monoxide.
Claims (4)
1. The application of the molybdenum modified zirconium dioxide material as a photocatalyst in the field of photocatalytic reduction of carbon dioxide is characterized in that the preparation method of the molybdenum modified zirconium dioxide comprises the following steps:
1) weighing a molybdenum source to prepare a molybdenum source aqueous solution;
2) taking a molybdenum source water solution, adding a zirconium source into the molybdenum source water solution, and uniformly stirring to obtain a mixed solution;
3) reacting the mixed solution obtained in the step 2) at 170-250 ℃ for 6-24 hours, and naturally cooling to room temperature after the reaction is finished, and leaving a lower-layer precipitate;
4) washing the precipitate to be neutral, and then drying to obtain a molybdenum modified zirconium dioxide material, wherein the ratio of the mass of molybdenum atoms to the mass of zirconium dioxide is 0.1-1%;
the drying temperature in the step 4) is 50-80 ℃, and the drying time is 5-24 hours;
the molybdenum modified zirconium dioxide material is a crystal and has monoclinic phase m-ZrO2And tetragonal phase t-ZrO2Two crystalline phases.
2. The use of claim 1, wherein the molybdenum source is sodium molybdate dihydrate, ammonium paramolybdate tetrahydrate, or molybdenum nitrate pentahydrate.
3. Use according to claim 1, wherein the zirconium source is zirconium nitrate pentahydrate, zirconium oxychloride, zirconium tetrachloride or zirconyl nitrate.
4. Use according to claim 1, characterized in that in step 4), the washing is carried out several times, in particular with deionized water and absolute ethanol.
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| CN201910563536.7A CN110237836B (en) | 2019-06-26 | 2019-06-26 | Molybdenum modified zirconium dioxide material and preparation method and application thereof |
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| CN102896317A (en) * | 2012-10-23 | 2013-01-30 | 上海大学 | Method for preparing Mo-ZrO2 metal ceramic electrode by utilizing sol-gel method |
| CN103611551A (en) * | 2013-11-21 | 2014-03-05 | 镇江市高等专科学校 | Preparation method of bismuth sulfide/bismuth molybdenum oxide heterojunction photocatalytic composite material |
| WO2017211712A1 (en) * | 2016-06-06 | 2017-12-14 | Huntsman P&A Germany Gmbh | Titanium dioxide sol, method for preparation thereof and products obtained therefrom |
| CN109364956A (en) * | 2018-11-15 | 2019-02-22 | 厦门大学 | A kind of preparation method and applications of high activity molybdenum sulfide-zirconia catalyst |
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| CN102896317A (en) * | 2012-10-23 | 2013-01-30 | 上海大学 | Method for preparing Mo-ZrO2 metal ceramic electrode by utilizing sol-gel method |
| CN103611551A (en) * | 2013-11-21 | 2014-03-05 | 镇江市高等专科学校 | Preparation method of bismuth sulfide/bismuth molybdenum oxide heterojunction photocatalytic composite material |
| WO2017211712A1 (en) * | 2016-06-06 | 2017-12-14 | Huntsman P&A Germany Gmbh | Titanium dioxide sol, method for preparation thereof and products obtained therefrom |
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