CN111974409A - Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof - Google Patents
Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof Download PDFInfo
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- CN111974409A CN111974409A CN202010815314.2A CN202010815314A CN111974409A CN 111974409 A CN111974409 A CN 111974409A CN 202010815314 A CN202010815314 A CN 202010815314A CN 111974409 A CN111974409 A CN 111974409A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 21
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006735 epoxidation reaction Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- LAZPBGZRMVRFKY-HNCPQSOCSA-N Levamisole hydrochloride Chemical compound Cl.C1([C@H]2CN3CCSC3=N2)=CC=CC=C1 LAZPBGZRMVRFKY-HNCPQSOCSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229960003734 levamisole hydrochloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002107 nanodisc Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof. The catalyst is in a flaky porous structure, wherein the atomic ratio of Mn to Ni is 0.019: 1-0.086: 1, and the catalyst comprises the following steps: and (3) taking the flaky NiO as a precursor, carrying out manganese doping by soaking manganese nitrate tetrahydrate, and roasting at a certain temperature to obtain the flaky porous manganese-doped nickel oxide catalyst. The catalyst shows excellent reaction effect in the selective oxidation reaction of styrene, and comprises higher reaction activity, higher product selectivity, good recycling performance and the like.
Description
Technical Field
The invention relates to a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof, and belongs to the technical field of preparation of organic reaction catalysts.
Background
The epoxy phenylethane is used as an important intermediate of medicines and spices, can be used as an epoxy resin diluent, a flavoring agent and a stabilizing agent, and is widely applied to the preparation of phenethyl alcohol, levamisole hydrochloride and the like.
At present, the traditional halohydrin method and peroxy acid direct oxidation method are mainly adopted for preparing epoxyphenylethane industrially, but the problems of high material cost, equipment corrosion, environmental pollution and the like exist. In order to solve the problems of the conventional methods, in recent years, extensive attention has been paid to a method for producing styrene oxide by performing styrene epoxidation reaction by using an environmentally-friendly, economical and reasonable catalytic system. For example, Chinese patent CN101181687A discloses Ag-Fe3O4Magnetic nano-catalyst and application in styrene epoxidation. The catalyst comprises Ag and Fe, wherein Ag is a specific active component, and is prepared by a solvothermal method. Although the catalyst has better catalytic activity in the styrene epoxidation reaction, the Ag as a noble metal element has limited reserves and higher price, and further application of the Ag is limited. In various catalysts studied at present, metalloporphyrin complexes have complex structures and more factors influencing the activity of the metalloporphyrin complexes, heteropoly acid catalysts and noble metal catalysts have high cost, and metal oxide catalysts have relatively simple preparation conditions and relatively low economic cost, so that great attention is paid to the metalloporphyrin complexes. However, the reaction performance of a simple metal oxide catalyst in the selective oxidation of styrene is still far from the same as that of other catalyst systems. For example, the publication of Catal. Commun. 10 (2008) 205-; the document mater. lett. 80 (2012) 23-25 uses NiO hollow nanodiscs for the selective oxidation of styrene with an epoxystyrene yield of 53.8%; the document Micropor, Mesopor, Mater, 238 (2017) 69-77 adopts a complex preparation method to embed NiO nano-particles in mesoporous SiO2When the catalyst is used for the selective oxidation of styrene, the yield of epoxy styrene is 63.0 percent. Therefore, how to upgrade and modify the metal oxide catalyst by a simple and effective method to improve the reaction performance of the metal oxide catalyst has very important significance.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: the manganese-doped nickel oxide catalyst is in a flaky porous structure, wherein the atomic ratio of Mn to Ni is 0.019: 1-0.086: 1.
The preparation method of the flaky porous manganese-doped nickel oxide catalyst comprises the following steps:
(1) the flaky NiO was dispersed in a mixed solution of deionized water and ethanol, and then a certain amount of polyvinylpyrrolidone (PVP,K30) and stirring uniformly;
(2) adding manganese nitrate tetrahydrate into the solution, and continuously stirring at 60 ℃ until the solution is completely evaporated to dryness;
(3) and drying the obtained powder at 100 ℃ for 12 h, and then roasting the powder in the air at 500-700 ℃ for 2-4 h to obtain the flaky porous manganese-doped nickel oxide catalyst.
Preferably, in the step (1), the volume ratio of water to ethanol is 1: 1.
Preferably, in the step (1), the mass ratio of NiO to polyvinylpyrrolidone is 1: 1.
Preferably, in the step (2), the mass ratio of the manganese nitrate tetrahydrate to the NiO is 0.12: 1-0.47: 1.
Preferably, in the step (3), the calcination temperature of the catalyst is 600 ℃, and the calcination time is 3 h.
The invention also provides application of the flaky porous manganese-doped nickel oxide catalyst in preparation of styrene oxide through selective oxidation of styrene.
The reaction process is as follows: uniformly mixing styrene, acetonitrile and tert-butyl hydroperoxide, then adding the prepared catalyst, and reacting for a period of time at a certain temperature to obtain the target product styrene oxide.
Preferably, the amount of the catalyst is 3.2-12.8 wt.% of styrene.
Preferably, the reaction temperature is 60-90 ℃.
Preferably, the reaction time is 6-10 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the flaky porous manganese-doped nickel oxide catalyst is simple and has low preparation cost.
(2) The catalytic system of the invention has simple reaction conditions, does not add any solvent or additive, takes tert-butyl hydroperoxide as an oxidant and is environment-friendly.
(3) The reaction effect of the sheet-shaped porous manganese-doped nickel oxide catalyst synthesized by the method is obviously superior to that of an undoped nickel oxide catalyst, the catalytic effect is not obviously reduced after the catalyst is repeatedly used for many times, and the stability is good; under the same reaction condition, the comprehensive catalytic performance of the catalyst is obviously superior to that of the related catalytic system reported at present, and the catalyst has good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of the flaky porous manganese-doped nickel oxide (Mn-NiO) catalysts prepared in examples 1 to 4 of the present invention.
FIG. 2 is an SEM image of an Mn-NiO-2 catalyst prepared in example 1 of the present invention.
FIG. 3 is a HRTEM image of the Mn-NiO-2 catalyst prepared in example 1 of the present invention.
FIG. 4 is an SEM image of an Mn-NiO-1 catalyst prepared in example 2 of the present invention.
FIG. 5 is an SEM image of an Mn-NiO-3 catalyst prepared in example 3 of the present invention.
FIG. 6 is an SEM image of an Mn-NiO-4 catalyst prepared in example 4 of the present invention.
Detailed Description
The technical solution of the present invention is explained in detail below with reference to the accompanying drawings and examples.
Example 1
0.5 g of the flaky NiO powder was weighed out and dispersed in a mixed solvent (20 mL of deionized water and 20 mL of ethanol), followed by addition of 0.5 g of polyvinylpyrrolidone (PVP,K30) and stirred until uniform. Then 0.117 g Mn (NO) was added3)2·4H2O, stirring at the constant temperature of 60 ℃ until the solution is evaporated to dryness, then drying at 100 ℃ for 12 h, roasting at 600 ℃ for 3 h under the air condition,the flaky porous manganese-doped nickel oxide catalyst is obtained and is marked as Mn-NiO-2. The inductively coupled plasma-atomic emission spectroscopy test shows that the atomic ratio of Mn to Ni is 0.030: 1.
The prepared catalyst is used for the selective oxidation reaction of styrene. First, 1.56 g of styrene, 6.24 g of t-butyl hydroperoxide and 16 mL of acetonitrile were mixed, 0.1 g of Mn-NiO-2 catalyst was added, the mixture was reacted in a constant temperature water bath at 80 ℃ for 8 hours, and the product was analyzed by gas chromatography, whereby it was found that the conversion of styrene reached 96.4% and the selectivity of ethylene oxide reached 77.8%. In addition, in order to test the recycling performance of the catalyst, the reacted catalyst was filtered off, and sufficiently washed with hot water and acetone, and then dried at 100 ℃ for 24 hours, and then used for the next test. As a result, the Mn-NiO-2 catalyst is not obviously reduced in catalytic activity and selectivity to the styrene oxide after being recycled for five times.
The XRD pattern of the Mn-NiO-2 catalyst prepared in example 1 is contained in FIG. 1.
FIG. 2 is an SEM image of the Mn-NiO-2 catalyst prepared in example 1.
FIG. 3 is a HRTEM image of the Mn-NiO-2 catalyst prepared in example 1.
Comparative example 1
In example 1, a blank experiment was performed, i.e. without the addition of catalyst, showing that: the styrene conversion was 17.9% and the styrene oxide selectivity was 72.2%.
Comparative example 2
The flake NiO was used directly as a catalyst for performance testing under the same reaction conditions as in example 1, and the results show that: the styrene conversion was 31.5% and the styrene oxide selectivity was 76.2%.
Example 2
Example 1 was repeated, except that 0.058 g of Mn (NO) was added3)2·4H2And O is added into the preparation system to obtain the Mn-NiO-1 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 89.2 percent, and the selectivity of the epoxyphenylethane reaches 74.4 percent.
The XRD pattern of the Mn-NiO-1 catalyst prepared in example 2 is contained in FIG. 1.
FIG. 4 is an SEM image of the Mn-NiO-1 catalyst prepared in example 2.
Example 3
Example 1 was repeated, except that 0.175 g of Mn (NO) was added3)2·4H2And O is added into the preparation system to obtain the Mn-NiO-3 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 91.2, and the selectivity of the epoxyphenylethane reaches 66.7 percent.
The XRD pattern of the Mn-NiO-3 catalyst prepared in example 3 is contained in FIG. 1.
FIG. 5 is an SEM image of the Mn-NiO-3 catalyst prepared in example 3.
Example 4
Example 1 was repeated, except that 0.233 g of Mn (NO) was added3)2·4H2And O is added into the preparation system to obtain the Mn-NiO-4 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 67.5 percent, and the selectivity of the epoxyphenylethane reaches 78.0 percent.
The XRD pattern of the Mn-NiO-4 catalyst prepared in example 4 is contained in FIG. 1.
FIG. 6 is an SEM image of the Mn-NiO-4 catalyst prepared in example 4.
Example 5
Example 1 was repeated except that the temperature of the styrene epoxidation reaction was set to 60 c, at which time the styrene conversion reached 42.5% and the styrene oxide selectivity reached 54.4%.
Example 6
Example 1 was repeated except that the temperature of the styrene epoxidation reaction was set to 90 c, at which the styrene conversion reached 99.1% and the styrene oxide selectivity reached 72.3%.
Example 7
Example 1 was repeated except that the reaction time was 6 hours, at which point the styrene conversion reached 82.9% and the styrene oxide selectivity reached 80.4%.
Example 8
Example 1 was repeated except that the reaction time was 10 hours, at which time the styrene conversion reached 99.4% and the styrene oxide selectivity reached 70.7%.
Example 9
Example 1 was repeated except that t-butyl hydroperoxide was added in an amount of 2.08 g, at which point the styrene conversion reached 49.6% and the styrene oxide selectivity reached 76.0%.
Example 10
Example 1 was repeated except that t-butyl hydroperoxide was added in an amount of 8.32 g, at which time the styrene conversion reached 94.7% and the styrene oxide selectivity reached 74.1%.
Example 11
Example 1 was repeated, except that 0.05 g of NiO/NMO-2 catalyst was added, at which point the styrene conversion reached 70.8% and the ethylene oxide selectivity reached 77.6%.
Example 12
Example 1 was repeated, except that 0.20 g of NiO/NMO-2 catalyst was added, at which point the styrene conversion reached 99.9% and the ethylene oxide selectivity reached 59.1%.
It will be readily appreciated by those skilled in the art that the above-described embodiments are merely illustrative of the present invention and are not intended to limit the present invention, and any extension, modification, replacement, improvement, etc. made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The manganese-doped nickel oxide catalyst is characterized by being in a sheet-shaped porous structure, wherein the atomic ratio of Mn to Ni is 0.019: 1-0.086: 1.
2. A preparation method of a manganese-doped nickel oxide catalyst comprises the following steps:
(1) dispersing the flaky NiO in a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone, and uniformly stirring;
(2) adding manganese nitrate tetrahydrate into the solution, and continuously stirring at 60 ℃ until the solution is completely evaporated to dryness;
(3) and drying the obtained powder at 100 ℃ for 12 h, and then roasting the powder in the air at 500-700 ℃ for 2-4 h to obtain the manganese-doped nickel oxide catalyst.
3. The method of claim 2, wherein in step (1), the volume ratio of deionized water to ethanol is 1: 1.
4. The method of claim 2, wherein in step (1), the mass ratio of NiO to polyvinylpyrrolidone is 1: 1.
5. The method according to claim 2, wherein in the step (2), the mass ratio of the manganese nitrate tetrahydrate to the NiO is 0.12:1 to 0.47: 1.
6. Use of the manganese-doped nickel oxide catalyst of claim 1 in the selective oxidation of styrene to styrene oxide.
7. The use according to claim 6, wherein the reaction is carried out by: styrene, acetonitrile and tert-butyl hydroperoxide are evenly mixed, manganese-doped nickel oxide catalyst is added, and the target product styrene oxide is prepared after reaction for a period of time at a certain temperature.
8. The use of claim 7, wherein the manganese-doped nickel oxide catalyst is present in an amount of 3.2 to 12.8 wt.% of the styrene.
9. The use according to claim 7, wherein the reaction temperature is 60 to 90 ℃.
10. The use according to claim 7, wherein the reaction time is 6 to 10.
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| CN112517021A (en) * | 2020-12-09 | 2021-03-19 | 扬州大学 | Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof |
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|---|---|
| CN111974409B (en) | 2022-10-28 |
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