CN116212854A - La (La) 1-x K x MnO 3 Perovskite preparation method and application thereof in preparing aldehyde by selectively oxidizing organic alcohol with molecular oxygen - Google Patents
La (La) 1-x K x MnO 3 Perovskite preparation method and application thereof in preparing aldehyde by selectively oxidizing organic alcohol with molecular oxygen Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 title abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002121 nanofiber Substances 0.000 claims abstract description 29
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 28
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 17
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims description 11
- 239000004323 potassium nitrate Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- YSLBFFIVJGJBSA-UHFFFAOYSA-N (4-ethylphenyl)methanol Chemical compound CCC1=CC=C(CO)C=C1 YSLBFFIVJGJBSA-UHFFFAOYSA-N 0.000 claims description 2
- JJCKHVUTVOPLBV-UHFFFAOYSA-N 3-Methylbenzyl alcohol Chemical compound CC1=CC=CC(CO)=C1 JJCKHVUTVOPLBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
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- 238000004627 transmission electron microscopy Methods 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
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- 150000002926 oxygen Chemical class 0.000 description 2
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- 238000003980 solgel method Methods 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 p-nitrophenyl alcohol Chemical compound 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 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
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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Abstract
The invention belongs to the technical field of catalysts, and particularly discloses preparation of a nanofiber tubular perovskite oxide with an exposed (110) high-energy surface and application of the nanofiber tubular perovskite oxide in preparing aldehyde by catalyzing molecular oxygen to selectively oxidize organic alcohol. The method comprises the steps of dissolving metal nitrate and polyvinylpyrrolidone in a mixed solution of water and N, N-dimethylformamide, and calcining and synthesizing the mixture at a high temperature in a muffle furnace by adopting an electrostatic spinning technology to obtain the nanofiber tubular perovskite oxide with the exposed (110) high-energy surface. Under normal pressure, oxygen gas flow is introduced as an oxidant, and when the reaction temperature is 50 ℃, the nanofiber tubular perovskite oxide with the exposed (110) high energy surface is selectively oxidized to benzyl alcohol to generate benzaldehyde, the conversion rate is as high as 93.6%, and the selectivity is kept to be more than 93.1%. The method has the advantages of simple process, low cost, environment-friendly preparation process and easy industrialization, and the obtained product has excellent reaction performance when being used for preparing the aldehyde by selectively catalyzing and oxidizing the organic alcohols at low temperature and normal pressure, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nanofiber tubular La with an exposed (110) high-energy surface 1-x K x MnO 3 A preparation method of perovskite and application of perovskite as a catalyst in preparing aldehyde by catalyzing molecular oxygen to oxidize organic alcohol.
Background
Benzaldehyde is used as an important fine chemical intermediate and is widely applied to chemical industries such as synthetic pesticides, essence and spice, medicines and the like. The traditional method adopts toluene chlorination hydrolysis to prepare benzaldehyde, but severely pollutes the environment, production equipment is easy to corrode, and products often incorporate trace chlorine, so that the wide application of the benzaldehyde in industries such as medicines and the like is limited.
Organic alcohol is used as a raw material, and organic aldehyde products can be efficiently produced through selective catalytic oxidation reaction, and common catalysts comprise noble metals, transition metal oxides and the like. The noble metal catalyst is used for organic alcohol and has excellent selective catalytic oxidation performance, but the price is high, and noble metal nano particles are easy to aggregate or leach out and run off in the catalytic reaction process, so that the catalytic activity is suddenly reduced; particularly, strong alkaline substances (such as KOH) are required to be added for reaction, so that the catalytic oxidation reaction device has good corrosion resistance, and the device cost of production equipment is greatly increased. Therefore, the development of the catalyst material with low cost, convenient reaction device and stable catalytic performance is a hot spot and difficult problem to be solved urgently at present.
Perovskite composite metal oxide (ABO) 3 ) Has excellent hydrothermal stability and better catalytic performance when used as a catalyst for selective oxidation reaction of organic alcohol. We have reported a sol Ce doped LaCoO 3 For the reaction of selectively catalyzing and oxidizing benzyl alcohol under normal pressure, 95 percent of benzyl alcohol conversion rate can be realized at the reaction temperature of 88 ℃ by taking oxygen as an oxidant (J.Catal.2016, 340, 41-48), which shows that the perovskite composite metal oxide is used for catalysisThe chemical molecular oxygen oxidation benzyl alcohol reaction has good application prospect. By O 2 As an oxidizing agent, a reaction by-product (H 2 O) has no pollution and easy separation, and is suitable for the environment-friendly and sustainable development of chemical industry concepts. However, the perovskite oxide needs to be calcined at a high temperature, so that the specific surface area is extremely small, the contact area with a catalytic reaction substrate is small, and the perovskite oxide is limited to exert high-efficiency catalytic performance. In addition, perovskite oxide prepared by the traditional method is in a disordered agglomeration form into a block shape in a high-temperature process, and the surface of large particles is exposed with various crystal faces, so that the preparation of the perovskite oxide catalyst with the exposed specific high-energy surface can not be completely realized. Aiming at the reaction of preparing aldehyde by oxidizing benzyl alcohol with molecular oxygen, how to controllably adjust and expose the specific high energy surface of perovskite, realize the reaction of catalyzing and oxidizing organic alcohols with high efficiency, reduce the reaction temperature, meet the requirements of selective oxidation chemical industry, and is a key problem for widely promoting the industrial application of perovskite oxide.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for preparing the nanofiber tubular perovskite material with low cost, simple preparation process, environmental friendliness and specific high energy surface exposure. We have found that nanofibrous tubular perovskite oxides with exposed (110) high energy surfaces can be obtained using electrospinning techniques. Oxygen is used as an oxidant, and the perovskite oxide is used as a catalyst to realize the high-efficiency selective catalysis of the organic alcohol to prepare aldehyde under the condition of normal pressure and low temperature of 50 ℃.
The technical scheme of the invention is as follows:
preparing a nanofiber tubular perovskite oxide (LaMnO) with an exposed (110) high energy surface by using metal nitrate and polyvinylpyrrolidone as precursors through an electrostatic spinning method 3 ) The preparation method and the application thereof in preparing aldehyde by catalyzing molecular oxygen to oxidize organic alcohol.
1. Nanofiber tubular perovskite oxide (La) with exposed (110) high energy surface 1-x K x MnO 3 ) The preparation method comprises the following steps:
(1) According to the stoichiometric ratio, dissolving lanthanum nitrate, potassium nitrate and manganese nitrate in a mixed solvent formed by distilled water and N, N-dimethylformamide, fully stirring for 3 hours, then adding polyvinylpyrrolidone which is equal to the total mass of the lanthanum nitrate, the potassium nitrate and the manganese nitrate, and stirring for 12 hours to form spinning precursor liquid;
the mixed solvent is formed by mixing distilled water and N, N-dimethylformamide according to the volume ratio of 6:25;
the solid-liquid ratio of the manganese nitrate to the mixed solvent is 10 mmol/31 mL;
the total molar weight of the lanthanum nitrate and the potassium nitrate is 1:1, and the total molar weight of the lanthanum nitrate and the potassium nitrate is 0-0.08:1.
(2) Filling spinning precursor liquid in a syringe, installing the syringe in an electrostatic spinning machine, starting electrostatic spinning at a propulsion speed of 0.5mL/h under 20kV voltage, and collecting a solid film on a receiving plate after spinning is finished;
(3) Transferring the collected film into a muffle furnace, heating to 700 ℃ from room temperature at 2 ℃/min, maintaining for 2h, and cooling to room temperature to obtain nanofiber tubular La with exposed (110) high-energy surface 1-x K x MnO 3 (0≤x≤0.08)。
2. The product obtained by the preparation method is used as a catalyst for catalyzing molecular oxygen to oxidize organic alcohol to prepare aldehyde, and the application of the catalyst is that:
the experimental set-up was a 25mL three-necked flask. The left neck is connected with an oxygen gas guide pipe, a flow controller is arranged at the front end, the flow rate is kept at 50mL/min, the middle neck is connected with a condensing pipe, and the right neck is connected with an injector. To a three-necked flask, 20. Mu.L of benzyl alcohol, 20. Mu.L of dodecane (an internal standard substance), 20mL of toluene (a solvent) and 100mg of a catalyst were placed, and after the reaction solution temperature was kept constant at 50℃by a magnetic heating stirrer, oxygen was introduced and stirred, and after a certain period of time, the sample was sampled by a syringe, separated, filtered and analyzed by gas chromatography.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The high-energy surface of perovskite is accurately controlled, and the preparation method is simple. In the prior art, the perovskite oxide is prepared, so that nano particles with various exposed crystal faces are often stacked, and great difficulty exists in realizing ordered arrangement of particles with single exposed high-energy faces. The invention applies the electrostatic spinning technology, and reports the successful synthesis of the nanofiber tubular perovskite oxide with the (110) crystal face exposed for the first time.
(2) The catalyst has simple preparation process, no need of special raw materials and conditions, and low raw material cost.
(3) The selective catalytic oxidation reaction uses oxygen as an oxidant, the generated by-product is water, and the target product is convenient and quick to separate and is environment-friendly.
(4) The selective catalytic oxidation reaction condition is mild, the operation is easy, the conversion rate of the benzyl alcohol can be higher than 93.6% under the condition of normal pressure and low temperature (50 ℃), and the selectivity of the benzaldehyde is kept to be higher than 93.1%.
Drawings
FIG. 1- (a) shows LaMnO prepared in example 1 3 (LaMnO 3 -NFT) XRD pattern; (b) The nanofibers prepared for examples 1 and 2 were tubular La 1-x K x MnO 3 XRD spectrum of (x= 0,0.01,0.05,0.08);
FIG. 2-LaMnO prepared in example 1 3 (LaMnO 3 -NFT) of (a) a scanning electron micrograph and (b) a transmission electron micrograph; (c) And (d) La prepared in example 2 0.95 K 0.05 MnO 3 Bulk and La 0.95 K 0.05 MnO 3 NFT transmission electron microscopy.
FIG. 3-LaMnO prepared in example 1 3 -NFT and LaMnO 3 Bulk (a) N 2 Adsorption-desorption isotherm curve and (b) pore size distribution map and (c) H 2 -TPR and (d) O 2 -TPD map.
FIG. 4- (a) is a nanofiber tubular LaMnO prepared in example 1 3 (LaMnO 3 -NFT) and bulk LaMnO 3 (LaMnO 3 Bulk) a graph of the selective catalytic benzyl alcohol oxidation activity; (b) The nanofibers prepared for examples 1 and 2 were tubular La 1-x K x MnO 3 (x= 0,0.01,0.05,0.08) a graph of change in catalytic oxidation benzyl alcohol reactivity; (c) La prepared for example 2 0.95 K 0.05 MnO 3 NFT catalytic oxidation of benzyl alcoholAlcohol activity as a function of oxygen concentration; (d) La prepared for example 2 0.95 K 0.05 MnO 3 NFT cyclic catalytic oxidation benzyl alcohol activity profile.
FIG. 5-O 2 The molecule (a) exists alone and is adsorbed on LaMnO 3 (012) When on crystal face and (b) exist separately and are adsorbed on LaMnO 3 (110) Bond length and corresponding adsorption energy when on the crystal face.
Detailed Description
The following applicant will describe the process of the present invention in detail in connection with specific examples to provide a further understanding of the invention to those skilled in the art, but the following examples are not to be construed in any way as limiting the scope of the invention.
In the examples below, lanthanum nitrate and manganese nitrate were used as La (NO 3 ) 3 ·6H 2 O、Mn(NO 3 ) 2 ·6H 2 O, potassium nitrate is anhydrous KNO 3 And (3) powder.
The polyvinylpyrrolidone used was PVP K30.
Example 1a method for preparing a nanofiber tubular perovskite oxide with an exposed (110) high energy surface, comprising the steps of:
a) Adding 10mmol of lanthanum nitrate and 10mmol of manganese nitrate into a mixed solvent formed by 6mL of distilled water and 25mL of N, N-dimethylformamide, fully stirring for 3h, then adding polyvinylpyrrolidone with the same mass as the total mass of the lanthanum nitrate and the manganese nitrate, and then stirring for 12h to form spinning precursor liquid;
b) Filling 10mL of spinning precursor liquid in a syringe, installing the syringe in an electrostatic spinning machine, starting electrostatic spinning at a propulsion speed of 0.5mL/h under 20kV voltage, and collecting a solid film on a receiving plate after spinning is finished;
c) Transferring the collected solid film into a muffle furnace, heating to 700 ℃ from room temperature at 2 ℃/min, maintaining for 2 hours, and cooling to room temperature to obtain the nanofiber tubular LaMnO with the exposed (110) high energy surface 3 Material (named LaMnO) 3 -NFT)。
Comparative example 1a conventional sol-gel process for preparing perovskite oxide particles comprises the following steps:
a) Lanthanum nitrate (10 mmol) and manganese nitrate (10 mmol) are added into distilled water (6 mL) for stirring and dissolution, and the mixture is evaporated to dryness under the water bath condition of 80 ℃ to form gel;
b) Placing into a drying oven at 100deg.C for 48 hr, transferring into a muffle furnace, heating to 700deg.C at 2deg.C/min, maintaining for 2 hr, and cooling to room temperature to obtain nanometer granular LaMnO 3 Material (named LaMnO) 3 -bulk)。
Instrumental characterization of the product:
a) Nanofiber tubular LaMnO obtained on X-ray diffractometer (Japanese society, ultima IV type) with Cu K alpha of X-ray source and scanning rate of 10 DEG/min 3 The X-ray diffraction (XRD) pattern of (C) is shown in figure 1a. And comparing the standard card, and indicating that the perovskite oxide is successfully synthesized by the electrostatic spinning method.
b) The nanofiber tubular LaMnO was subjected to Scanning Electron Microscopy (SEM) (Hitachi SU 8010, japan) and Transmission Electron Microscopy (TEM) (FEI, tecnai F20, U.S.A.) 3 The microscopic morphology observation of the sample, see fig. 2a-b, confirms the generation of the tubular morphology of the nanofibers, which is formed by orderly stacking of the nanoparticles.
c) LaMnO prepared by the two methods is tested on a physical adsorption instrument (Beijing Bei Shide, 3H-2000PS 2) 3 The specific surface area and pore volume of the sample are shown in figures 3a-b. LaMnO obtained by two methods 3 The specific surface area and the pore volume are close, and the nano particles are piled up, so that the pore size distribution formed by piling up is wide.
d) LaMnO obtained by the above two methods was tested by using a chemisorber (Hunan Hua Sai, DAS-7000) 3 Redox properties are shown in FIGS. 3c-d. Compared with LaMnO 3 -bulk，LaMnO 3 The reduction temperature of the NFT is reduced, and the desorption oxygen content is higher, which indicates that the nanofiber tubular LaMnO 3 The reducible capacity is increased and the activated oxygen capacity is increased.
Example 2:
to expand the application of the electrostatic spinning method in preparing the LaMnO-removing material 3 Other Mn series nano fiber tubular perovskite oxide, laMnO doped with a small amount of K ions at A position is selected 3 Is the study object. Lanthanum nitrate (9.5 mmol), potassium nitrate (0.5 mmol) and manganese nitrate (10 mmol) were added to a mixed solvent of distilled water (6 mL) and N, N-dimethylformamide (25 mL), and stirred well for 3 hours. Preparation of nanofiber tubular LaMnO by the subsequent step and the electrospinning method of example 1 3 The NFT is consistent, and the obtained product is named La 0.95 K 0.05 MnO 3 -NFT。
Changing the addition amount of lanthanum nitrate and potassium nitrate according to the stoichiometric ratio, and obtaining La respectively in the rest preparation process same as the above 0.99 K 0.01 MnO 3 -NFT，La 0.92 K 0.08 MnO 3 -NFT. Reference LaMnO in comparative example 1 3 Preparation method of bulk, preparing La by sol-gel method 0.95 K 0.05 MnO 3 -bulk。
Instrumental characterization of the product:
a) La obtained by doping K ions at A position 1-x K x MnO 3 The X-ray diffraction (XRD) pattern of the NFT (x= 0.01,0.05,0.08) is shown in fig. 1b. It is explained that the A-site K doping does not affect the formation of perovskite type oxides.
b) FIGS. 2c-d show La with particle packing 0.95 K 0.05 MnO 3 Bulk and nanofiber tubular La 0.95 K 0.05 MnO 3 Transmission electron microscopy of NFT confirmed nanofiber tubular La 0.95 K 0.05 MnO 3 The NFT exposes the (110) high energy plane.
Example 3:
100mg of LaMnO prepared in example 1 was weighed 3 NFT for selective catalytic oxidation reactions, the remaining steps being in accordance with the steps in the section "application in the catalytic oxidation of organic alcohols to aldehydes" of the previous summary. After 3h of reaction, the liquid sample was taken out and filtered, and the component content was quantitatively analyzed by a gas chromatograph (Agilent, 8890 GC), the conversion of benzyl alcohol (X BzOH (percent) selectivity of benzaldehyde product (S) BzH The calculation formula is as follows:
[BzOH] 0 and [ BzOH ]] t The concentrations of benzyl alcohol at reaction times 0 and t (h), respectively; [ BzH ]] t The concentration of benzaldehyde produced during the reaction time t (h) is shown.
Under the same conditions, laMnO is respectively tested 3 -bulk，LaMnO 3 -NFT，La 0.99 K 0.01 MnO 3 -NFT，La 0.95 K 0.05 MnO 3 NFT and La 0.92 K 0.08 MnO 3 The NFT catalytic oxidation benzyl alcohol reactivity corresponds to the results shown in fig. 4a-b, (1) in fig. 4b, the compounds denoted by x=0, 0.01,0.05,0.08 are LaMnO respectively 3 -NFT、La 0.99 K 0.01 MnO 3 -NFT、La 0.95 K 0.05 MnO 3 -NFT、La 0.92 K 0.08 MnO 3 NFT, (2) conversion and selectivity are respectively: laMnO 3 Bulk conversion 67.1%, selectivity 90.2%, laMnO 3 Conversion of NFT 81.4%, selectivity 93.5%, la 0.99 K 0.01 MnO 3 Conversion of NFT 87.3%, selectivity 92.1%, la 0.95 K 0.05 MnO 3 Conversion of NFT 93.6%, selectivity 93.1%, la 0.92 K 0.08 MnO 3 The conversion of NFT was 84.9%, selectivity 92.4%. The nanofiber tubular perovskite oxide exposed with the (110) crystal face shows excellent selective benzyl alcohol oxidation reaction performance, and the selective catalytic oxidation performance can further improve the yield to nearly 100% when a proper amount of K ions are doped at the A site.
Example 4:
oxygen is used as an oxidant for benzyl alcohol oxidation reaction, and the apparent rate of benzyl alcohol oxidation reaction is determined in order to verify the influence of concentration change on the activity of selective catalytic oxidation reaction and further reflect the capacity of activated oxygen. Tubular La with nanofibers 0.95 K 0.05 MnO 3 NFT is the research object, and the flow rate of the introduced oxidant is not highThe other conditions and steps were identical to those of example 3, except that the composition of the gas composition was changed. The composition change of the gas components is that two flowmeters are selected to respectively control the flow rates of the introduced nitrogen and the oxygen, the total flow rate is kept to be 50mL/min, the oxygen content in the final gas is respectively adjusted to be 20%,50%,80%, and the change of the catalytic oxidation performance is tested, as shown in a graph 4c (the conversion rate is 83.4% when the final gas is 20%, the selectivity is 93.7%, the conversion rate is 85.9% when the final gas is 50%, the selectivity is 93.1%, the conversion rate is 91.5% when the final gas is 80%, the conversion rate is 91.2% when the final gas is 100%, and the conversion rate is 93.6% when the final gas is 93.1%). This means that the oxygen concentration affects the catalytic oxidation performance, and that the oxygen adsorption-activation rate is slower, so that the overall apparent catalytic reaction rate is directly determined, and the stronger the adsorption-activation oxygen capability of the catalyst is, the more favorable the improvement of the selective catalytic oxidation performance.
Example 5:
testing of nanofiber tubular La 0.95 K 0.05 MnO 3 Cyclic catalytic oxidation performance of NFT. The reaction of example 2 was followed by filtration and drying in an oven at 100 c, and a plurality of parallel experiments were performed, in which the recovered catalyst was calcined in a muffle furnace at 420 c (a temperature selected based on the thermogravimetric result of the recovered catalyst for removing the organic substances adsorbed on the surface of the recovered catalyst, and only a medium temperature of 420 c was required to remove the organic substances), and then cooled. 0.1g of calcined catalyst was used to evaluate the performance of the selective catalytic benzyl alcohol oxidation reaction, and the process was the same as in example 3, and three cycle experiments were performed, see fig. 4d. With the increase of the cycle times, the conversion rate of the reactant benzyl alcohol is slightly reduced, but the selectivity of benzaldehyde is always kept higher than 90%, which indicates that the nanofiber tubular perovskite oxide has better cycle catalytic performance.
Example 6:
to confirm La 0.95 K 0.05 MnO 3 NFT and La 0.95 K 0.05 MnO 3 Bulk catalytic benzyl alcohol oxidation activity difference, O is calculated by Density Functional Theory (DFT) due to the difference of corresponding activating oxygen capacity of the surface exposed crystal face 2 Respectively adsorb on LaMnO 3 In the (012) and (110) crystal planes, the adsorption energy becomesChemical and O 2 The bond length varies. O (O) 2 When the molecule is adsorbed on a (110) crystal face, the adsorption energy is-7.73 eV; o (O) 2 The adsorption energy of the molecule at the (012) plane was-0.94 eV, indicating O 2 Easier in LaMnO 3 Is activated by the high energy surface (110). In addition, O 2 Free dissociation into O atoms is possible on the high energy surface (110), corresponding to the result of fig. 5.
Example 7:
to check La 0.95 K 0.05 MnO 3 NFT catalytic selective oxidation capability of other organic alcohols, six organic alcohols such as o-methyl benzyl alcohol, m-methyl benzyl alcohol, p-ethyl benzyl alcohol, DL-benzyl alcohol and p-nitrophenyl alcohol are selected as substrates, the addition amount of the substrates is 0.2mmol, other test steps and reaction conditions are the same as those of example 3, and the results are shown in Table 1, and La is shown 0.95 K 0.05 MnO 3 NFT is versatile in catalyzing selective oxidation of organic alcohols.
TABLE 1 La 0.95 K 0.05 MnO 3 NFT catalyzes different organic alcohol oxidation reaction properties.
Claims (7)
1. A method for preparing a nanofiber tubular perovskite oxide with an exposed (110) high energy surface, comprising the steps of:
(1) Dissolving lanthanum nitrate, potassium nitrate and manganese nitrate in a mixed solvent formed by distilled water and N, N-dimethylformamide, fully stirring, then adding polyvinylpyrrolidone with the same total mass as the lanthanum nitrate, the potassium nitrate and the manganese nitrate, and fully stirring to form spinning precursor liquid;
the mixed solvent is formed by mixing distilled water and N, N-dimethylformamide according to the volume ratio of 6:25;
the solid-to-liquid ratio of the manganese nitrate to the mixed solvent is 10 mmol/31 mL;
the total molar weight of the lanthanum nitrate and the potassium nitrate is 1:1, and the total molar weight of the lanthanum nitrate and the potassium nitrate is 0-0.08:1;
(2) Filling spinning precursor liquid in a syringe, installing the syringe in an electrostatic spinning machine, starting electrostatic spinning at a propulsion speed of 0.5mL/h under 20kV voltage, and collecting a solid film on a receiving plate after spinning is finished;
(3) Transferring the solid film collected in the step (2) into a muffle furnace, heating to 700 ℃ from room temperature at a heating rate of 2 ℃/min, maintaining for 2 hours, and cooling to room temperature to obtain the nanofiber tubular La with the exposed (110) high-energy surface 1-x K x MnO 3 Wherein x=0 to 0.08.
2. La prepared by the preparation method according to claim 1 1-x K x MnO 3 The catalyst is used for preparing organic aldehyde by catalytic oxidation of organic alcohol.
3. The use according to claim 2, characterized in that: the organic alcohol is benzyl alcohol, o-methyl benzyl alcohol, m-methyl benzyl alcohol, p-ethyl benzyl alcohol, DL-phenethyl alcohol and/or p-nitrobenzene methyl alcohol.
4. La prepared by the preparation method according to claim 1 1-x K x MnO 3 The catalyst is applied to the reaction of selectively catalyzing and oxidizing benzyl alcohol.
5. The use according to claim 4, wherein benzaldehyde is prepared by selective catalytic oxidation of benzyl alcohol.
6. The use according to claim 5, characterized in that: the reaction for preparing benzaldehyde by selectively catalyzing and oxidizing benzyl alcohol is carried out in toluene.
7. The use according to claim 5, characterized in that: the reaction for preparing benzaldehyde by selectively catalyzing and oxidizing benzyl alcohol is carried out at 50 ℃ and under normal pressure.
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