CN116870924A - Preparation method of spinel-structure high-entropy oxide nanofiber-based photocatalyst - Google Patents
Preparation method of spinel-structure high-entropy oxide nanofiber-based photocatalyst Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000011029 spinel Substances 0.000 claims abstract description 32
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 claims description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical group [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
Abstract
The invention discloses a preparation method of a spinel structure high-entropy oxide nanofiber-based photocatalyst, which comprises the following steps: firstly, weighing metal salt according to an equimolar ratio, dispersing the weighed metal salt in an organic solvent, and stirring to form a stable precursor solution; step two, adding a high molecular polymer into the precursor solution and stirring to form precursor sol; step three, precursor sol is subjected to electrostatic spinning technology to obtain precursor nanofibers; step four, drying the precursor fiber to form a stable precursor nanofiber; and fifthly, treating the precursor nanofiber by adopting a gradient calcination process to obtain the high-entropy oxide nanofiber-based photocatalyst. The preparation method of the spinel structure high-entropy oxide nanofiber-based photocatalyst has lower energy consumption and cost, can prepare the nanofiber with finer and more uniform grains, and can realize effective control of the structure by adjusting the calcination temperature.
Description
Technical Field
The invention relates to the technical field of environmental catalysis, in particular to a preparation method of a spinel structure high-entropy oxide nanofiber-based photocatalyst.
Background
The preparation method of the high-entropy oxide photocatalyst is one of research hotspots in the current photocatalysis field. The high entropy oxide material is a composite material composed of a plurality of metal elements, and has a highly complex structure and chemical composition. Compared to conventional semiconductor nanomaterials, high entropy oxides have many advantageous properties including a wider band gap energy range, a slower photo-generated electron-hole pair recombination rate, and excellent photocatalytic performance.
The invention patent CN202110501167.6 provides a preparation method of an Ag quantum dot modified high-entropy oxide photocatalyst. In past studies, the preparation of high entropy oxide materials has generally employed conventional synthetic methods such as solid phase reactions, solution processes, or physical vapor deposition. However, these methods have some limitations, such as high reaction temperature, high cost, complex preparation process, and the like, and the prepared catalyst has larger crystal grains and small specific surface area, which limits the application and popularization of the high-entropy oxide material.
Disclosure of Invention
The invention aims to provide a preparation method of a spinel structure high-entropy oxide nanofiber-based photocatalyst, which uses acetylacetonate as a metal source in a precursor, uses a sol-gel electrostatic spinning technology and combines a gradient calcination process to synthesize photocatalytic CO with adjustable shape at a lower temperature 2 Reduction catalyst for CO 2 Rapid reduction to CO and CH 4 。
In order to achieve the above purpose, the invention provides a preparation method of a spinel structure high entropy oxide nanofiber-based photocatalyst, which comprises the following steps:
step one, weighing any five or all six metal salts according to an equimolar ratio, dispersing the weighed metal salts in an organic solvent, and stirring for 24 hours to form a stable precursor solution;
step two, adding a high molecular polymer with the mass fraction of 1-2% into the precursor solution obtained in the step one, and stirring for 24 hours to form precursor sol;
step three, the precursor sol obtained in the step two is subjected to electrostatic spinning technology to obtain precursor nanofibers;
step four, drying the precursor fiber obtained in the step three in a blowing oven at 80 ℃ for 2 hours to form a stable precursor nanofiber;
and step five, treating the precursor nanofiber subjected to the drying treatment in the step four in air by adopting a gradient calcination process to obtain the high-entropy oxide nanofiber-based photocatalyst.
Preferably, the weight ratio of the metal source to the organic solvent in the precursor solution in the first step is 1:10-3:10, and the organic solvent in the precursor solution is a mixed solvent of ethanol, acetic acid and DMF in a mass ratio of 4:6:2.
Preferably, the metal atom in the metal salt in the first step is a transition metal Cu, co, ni, zn, fe, mn, and the metal sources used are all acetylacetonates, and the metal salt is specifically Ni (acac) 2 、Cu(acac) 2 、Mn(acac) 2 、Co(acac) 3 、Zn(acac) 2 、Fe(acac) 3 Any five or all six of these.
Preferably, the high molecular polymer in the second step is one or more of polyvinylpyrrolidone, polyvinyl alcohol and polyacrylonitrile, preferably polyvinylpyrrolidone.
Preferably, the gradient calcining process in the fifth step includes: heating from room temperature to 150-250deg.C at a heating rate of 5-10deg.C/min, and maintaining at 150-300deg.C for 30-180min; then the temperature is raised to 400-1000 ℃ from room temperature at the heating rate of 1-2 ℃/min, and is kept at 400-1000 ℃ for 0-360min, and then the temperature is naturally cooled down.
Preferably, the gradient calcining process in the fifth step can form three structures of nano fiber, hollow nano fiber and nano belt at different temperatures, and the diameter is between 200 and 500 nm.
Preferably, the process parameters of the electrospinning in the third step are as follows: the pouring speed is 1-2mL/h, the voltage is 20-30kV, and the receiving distance is 15-20cm.
Therefore, the preparation method of the spinel structure high-entropy oxide nanofiber-based photocatalyst has the following beneficial effects:
(1) Unlike the traditional preparation method of the high-entropy oxide, the invention provides the spinel structure high-entropy oxide nanofiber-based CO 2 The preparation method of the reduction photocatalyst has the advantages of low calcining temperature, simplicity, low cost and strong expandability. The method is environment-friendly and efficient, is suitable for large-scale production, and has good commercial application prospect.
(2) The spinel-structure high-entropy oxide nanofiber prepared by the invention has small diameter, high porosity and large specific surface area, and is CO 2 Reduction provides a rich active site.
(3) The spinel structure high-entropy oxide nanofiber prepared by the invention has the advantages of extremely high light absorption capacity, good heat resistance, corrosion resistance and the like, and has high catalytic activity due to the high entropy effect and cocktail effect.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an XRD test result of a spinel structure high entropy oxide nanofiber material containing any five or all six metal elements according to an embodiment of a preparation method of a spinel structure high entropy oxide nanofiber-based photocatalyst of the present invention;
FIG. 2 is a schematic diagram showing a band-like structure (NiCuMnCoZnFe) synthesized at 800℃according to an example of a method for preparing a spinel-structured high-entropy oxide nanofiber-based photocatalyst according to the present invention 3 O 4 SEM image of nanofibers;
FIG. 3 shows a band-like (NiCu) structure synthesized at 800℃in an example of a method for preparing a spinel structure high entropy oxide nanofiber-based photocatalyst according to the present inventionMnCoZnFe) 3 O 4 TEM image of nanofibers;
FIG. 4 shows a spinel structure high entropy oxide nanofiber based photocatalyst prepared according to an example of the present invention (NiCuMnCoZnFe) synthesized at 800 ℃ 3 O 4 The photocatalytic performance results of (2);
FIG. 5 is a schematic illustration of a spinel structure high entropy oxide nanofiber based photocatalyst of an embodiment of the present invention, synthesized hollow (NiCuMnCoZnFe) at 400 ℃ 3 O 4 SEM image of nanofibers;
FIG. 6 shows a bead (NiCuMnCoZnFe) synthesized at 1000℃according to an example of a method for preparing a spinel-structured high-entropy oxide nanofiber-based photocatalyst according to the present invention 3 O 4 SEM image of nanofibers.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The preparation method of the spinel structure high-entropy oxide nanofiber-based photocatalyst comprises the following specific steps:
(1) Preparing a precursor solution consisting of a metal source, a solvent and a polymer: ni (acac) was weighed at room temperature in equimolar ratio 2 、Cu(acac) 2 、Mn(acac) 2 、Co(acac) 3 、Zn(acac) 2 、Fe(acac) 3 Metal salt (aletin) and dispersed in the mass percentage of 4:6:2, acetic acid and DMF in a solvent mixture, for 24h. The total mass of the metal salt was 2g, and the mass of the solvent was 10g. After stirring uniformly, 1.85g of polyvinylpyrrolidone (Ala-dine, PVP, molecular weight 1300000) was dissolved in the prepared solution, and the precursor solution was prepared by stirring for 24 hours.
(2) The metal precursor solution prepared in step (1) was aspirated using a 10mL syringe, and the syringe was fixed on a syringe pump. The front end of the needle head is connected with the positive electrode clamp, the non-woven fabric receiving roller is connected with the negative electrode clamp, and the distance between the receiving roller and the stainless steel needle head is about 15cm. The positive pressure was set at 25kV, the negative pressure was set at-1 kV, and spinning was started at a flow rate of 1 mL/h. After spinning is completed, the collected precursor nanofibers are gently removed and placed in a forced air oven at about 80 ℃ for continuous drying for about 12 hours.
(3) And (3) putting the precursor nanofiber subjected to the drying treatment in the step (2) into a ceramic boat, transferring the ceramic boat into a muffle furnace, and carrying out annealing treatment in the muffle furnace. Setting a muffle furnace program: heating from room temperature to 200deg.C at a heating rate of 5deg.C/min, and then heating to 800deg.C at a heating rate of 1deg.C/min to obtain spinel Dan Gaoshang oxide (NiCuMnCoZnFe) 3 O 4 Nanofiber material, exhibiting a ribbon-like structure.
(4) Weigh 30mg (NiCuMnCoZnFe) 3 O 4 Deionized water was added in a volume of 10ml and was carried out in a quartz reactor equipped with a cooling system. After the reactants were well mixed, nitrogen was used to remove oxygen. Then irradiating with 300W Xe lamp (320-2500 nm), reacting for 1-4h, and subjecting CO and CH to gas chromatograph equipped with flame ionization detector 4 The gaseous products of (2) were analyzed for more than 1 h.
In step (2) of this embodiment, the positive pressure value of the positive electrode clip connected to the tip of the needle may also be set to 20kV, 22kV, 23kV. In step (3) of the present embodiment, the gradient temperature increase program may be further set to:
heating from room temperature to 200 ℃ at a heating rate of 5 ℃/min, and then heating to 800 ℃ at a heating rate of 2 ℃/min;
heating from room temperature to 200deg.C at a heating rate of 5deg.C/min, and then heating to 1000deg.C at a heating rate of 2deg.C/min.
FIG. 1 is an XRD pattern of the product of example 1 of the present invention, whose diffraction peaks correspond to the (110), (220), (311), (400) and (511) crystal planes of spinel, respectively, demonstrating that a single-phase solid solution of spinel structure was successfully synthesized in example 1 of the present invention.
Fig. 2 is a representation of the scanning electron microscope of the spinel structure high entropy oxide nanofiber in example one of the present invention, exhibiting nanoribbon structures with smooth surfaces and fine particles, the ribbon structures providing high active areas.
FIG. 3 is a representation of the transmission electron microscope of the spinel-structured high entropy oxide nanofiber in example one of the present invention, with a lattice fringe spacing of 0.484nm, corresponding to the (111) crystal plane of the spinel structure.
FIG. 4 is a spinel structure high entropy oxide nanofiber photocatalytic CO according to an embodiment of the present invention 2 Results of reduction properties. Wherein the CH4 yield was 10.64 umol/g.h and the CO yield was 20.34 umol/g.h.
Example two
The preparation method of the spinel structure high-entropy oxide nanofiber-based photocatalyst comprises the following specific steps:
(1) Preparing a precursor solution consisting of a metal source, a solvent, and a polymer: ni (acac) was weighed at room temperature in equimolar ratio 2 、Cu(acac) 2 、Mn(acac) 2 、Co(acac) 3 、Fe(acac) 3 Metal salt (aletin) and dispersed in the mass percentage of 4:6:2, acetic acid and DMF in a solvent mixture, for 24h. The total mass of the metal salt was 2g, and the mass of the solvent was 10g. After stirring uniformly, 1.85g of polyvinylpyrrolidone (Ala-dine, PVP, molecular weight 1300000) was dissolved in the prepared solution, and the precursor solution was prepared by stirring for 24 hours.
(2) The metal precursor solution prepared in step (1) was aspirated using a 10mL syringe, and the syringe was fixed on a syringe pump. The front end of the needle head is connected with the positive electrode clamp, the non-woven fabric receiving roller is connected with the negative electrode clamp, and the distance between the receiving roller and the stainless steel needle head is about 15cm. The positive pressure was set at 25kV, the negative pressure was set at-1 kV, and spinning was started at a flow rate of 1 mL/h. After spinning is completed, the collected precursor nanofibers are gently removed and placed in a forced air oven at about 80 ℃ for continuous drying for about 12 hours.
(3) And (3) putting the precursor nanofiber subjected to the drying treatment in the step (2) into a ceramic boat, transferring the ceramic boat into a muffle furnace, and carrying out annealing treatment in the muffle furnace. Setting a muffle furnace program: heating from room temperature to 200deg.C at a heating rate of 5deg.C/min, and then heating at 2deg.C/mThe temperature rise rate of in is heated to 400 ℃, and finally, the spinel Dan Gaoshang oxide (NiCuMnCoFe) is obtained 3 O 4 Nanofiber material, exhibiting a hollow structure.
(4) Weigh 30mg (NiCuMnCoFe) 3 O 4 Deionized water was added in a volume of 10ml and was carried out in a quartz reactor equipped with a cooling system. After the reactants were well mixed, nitrogen was used to remove oxygen. Then irradiating with 300W Xe lamp (320-2500 nm), reacting for 1-4h, and subjecting CO and CH to gas chromatograph equipped with flame ionization detector 4 The gaseous products of (2) were analyzed for more than 1 h.
FIG. 5 is a representation of the scanning electron microscope of the spinel structure high entropy oxide nanofiber in example two of the present invention, which shows a hollow structure, smooth surface, fine particles, and the hollow structure provides a high active area.
FIG. 6 is a representation of a scanning electron microscope of spinel structure high entropy oxide nanofibers obtained by calcining precursor fibers at 1000deg.C in example two of the present invention, exhibiting a beaded structure with larger grains.
Therefore, the preparation method of the spinel structure high-entropy oxide nanofiber-based photocatalyst has lower energy consumption and cost, can prepare the nanofiber with finer and more uniform grains, and can realize effective control of the structure by adjusting the calcination temperature. These properties improve the specific surface area light absorption properties of the photocatalyst.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (7)
1. A preparation method of a spinel structure high-entropy oxide nanofiber-based photocatalyst is characterized by comprising the following steps of: the method comprises the following steps:
step one, weighing any five or all six metal salts according to an equimolar ratio, dispersing the weighed metal salts in an organic solvent, and stirring for 24 hours to form a stable precursor solution;
step two, adding a high molecular polymer with the mass fraction of 1-2% into the precursor solution obtained in the step one, and stirring for 24 hours to form precursor sol;
step three, the precursor sol obtained in the step two is subjected to electrostatic spinning technology to obtain precursor nanofibers;
step four, drying the precursor fiber obtained in the step three in a blowing oven at 80 ℃ for 2 hours to form a stable precursor nanofiber;
and step five, treating the precursor nanofiber subjected to the drying treatment in the step four in air by adopting a gradient calcination process to obtain the high-entropy oxide nanofiber-based photocatalyst.
2. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the weight ratio of metal in the precursor solution in the first step to the organic solvent is 1:10-3:10, and the organic solvent in the precursor solution is a mixed solvent of ethanol, acetic acid and DMF (dimethyl formamide) in a mass ratio of 4:6:2.
3. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the metal atoms in the metal salt in the first step are transition metal Cu, co, ni, zn, fe, mn, the metal sources are all acetylacetonates, and the metal salt is Ni (acac) 2 、Cu(acac) 2 、Mn(acac) 2 、Co(acac) 3 、Zn(acac) 2 、Fe(acac) 3 Any five or all six of these.
4. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the high polymer in the second step is one or more of polyvinylpyrrolidone, polyvinyl alcohol and polyacrylonitrile, preferably polyvinylpyrrolidone.
5. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the gradient calcining process in the fifth step comprises the following steps: heating from room temperature to 150-250deg.C at a heating rate of 5-10deg.C/min, and maintaining at 150-300deg.C for 30-180min; then the temperature is raised to 400-1000 ℃ from room temperature at the heating rate of 1-2 ℃/min, and is kept at 400-1000 ℃ for 0-360min, and then the temperature is naturally cooled down.
6. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the gradient calcining process in the fifth step can form three structures of nano fiber, hollow nano fiber and nano belt at different temperatures, and the diameter is between 200 and 500 nm.
7. The method for preparing the spinel structure high-entropy oxide nanofiber-based photocatalyst according to claim 1, wherein the method comprises the following steps: the electrostatic spinning process parameters in the third step are as follows: the pouring speed is 1-2mL/h, the voltage is 20-30kV, and the receiving distance is 15-20cm.
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| CN107164838A (en) * | 2017-07-11 | 2017-09-15 | 电子科技大学 | The method for preparing Co base spinel oxide nano wires |
| CN114843493A (en) * | 2022-05-23 | 2022-08-02 | 合肥精创科技有限公司 | One-dimensional high-entropy oxide nano material and preparation method and application thereof |
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| CN107164838A (en) * | 2017-07-11 | 2017-09-15 | 电子科技大学 | The method for preparing Co base spinel oxide nano wires |
| CN114843493A (en) * | 2022-05-23 | 2022-08-02 | 合肥精创科技有限公司 | One-dimensional high-entropy oxide nano material and preparation method and application thereof |
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