CN116550336A - Pd doped perovskite oxide nanofiber as well as preparation method and application thereof - Google Patents
Pd doped perovskite oxide nanofiber as well as preparation method and application thereof Download PDFInfo
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- CN116550336A CN116550336A CN202310837850.6A CN202310837850A CN116550336A CN 116550336 A CN116550336 A CN 116550336A CN 202310837850 A CN202310837850 A CN 202310837850A CN 116550336 A CN116550336 A CN 116550336A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims description 40
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 33
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 27
- 238000006555 catalytic reaction Methods 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 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 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention belongs to the technical field of catalytic Suzuki coupling reaction, and provides Pd-doped perovskite oxide nanofiber, and a preparation method and application thereof 0.9 Pd x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2. The Pd-doped perovskite oxide nanofiber La is prepared by electrostatic spinning and high-temperature calcination 0.9 Pd x Co 0.7 Mn 0.3 O 3 (x=0.1 or 0.2), the perovskite catalyst is exposed to more active sites of central metal after being doped with Pd element, so that the Suzuki reaction process is accelerated, the carbon-carbon coupling activity of the Suzuki reaction is promoted, and the catalyst has good circulation stability.
Description
Technical Field
The invention relates to the technical field of catalytic Suzuki coupling reaction, in particular to Pd doped perovskite oxide nanofiber and a preparation method and application thereof.
Background
The Suzuki coupling reaction is widely applied to synthesizing biphenyl compounds, and has the advantages of simplicity and convenience in operation and the like. The Suzuki coupling reaction catalyzed by the transition metal palladium or nickel has wider selectivity to the substrate, mild reaction condition, less byproducts and easy processing of the product. The common palladium-supported catalysts, homogeneous catalysts and the like, and the carrier materials of the palladium-supported catalysts mainly comprise active carbon, metal oxide, aluminosilicate microporous molecular sieve, silica materials, active clay, polymers and the like. The preparation method of the supported palladium catalyst mainly comprises two steps, wherein one is realized by adsorbing palladium on the surface of a carrier, and the other is realized by grafting special functional groups on the surface of the carrier and then loading the palladium on the functional groups in a coordination mode. The supported palladium catalyst has the following defects: (1) In the catalytic reaction process, the loss phenomenon of active species palladium exists; (2) In general, their catalytic activity and stereoselectivity control ability are inferior to those of homogeneous catalysts. The homogeneous catalyst has high energy consumption when being used for Suzuki coupling reaction, pd-containing catalyst is difficult to recycle, biphenyl products and the catalyst are difficult to separate, and the problems of target product pollution, environmental pollution and the like are caused.
Therefore, the Pd doped catalyst which is simple and environment-friendly, low in energy consumption, good in recycling performance and easy to separate products from the catalyst is obtained by research, and has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide Pd-doped perovskite oxide nanofiber as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides Pd-doped perovskite oxide nanofiber, which is La 0.9 Pd x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2.
The invention also provides a preparation method of the Pd-doped perovskite oxide nanofiber, which comprises the following steps:
1) Polyvinylpyrrolidone solution, la (NO 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 O is mixed to obtain spinning precursor solution;
2) Carrying out electrostatic spinning on the spinning precursor solution to obtain a polyvinylpyrrolidone nanofiber membrane;
3) Calcining the polyvinylpyrrolidone nanofiber membrane to obtain La 0.9 Pd x Co 0.7 Mn 0.3 O 3 。
Preferably, the solvent of the polyvinylpyrrolidone solution in the step 1) is N, N-dimethylformamide, and the mass fraction of polyvinylpyrrolidone in the polyvinylpyrrolidone solution is 10-14%.
Preferably, when the Pd-doped perovskite oxide nanofiber is La 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 2.85-2.97: 0.14-0.23: 0.5 to 0.61: 1.5-1.55;
when the Pd doped perovskite oxide nanofiber is La 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 2.85-2.97: 0.32-0.42: 0.5 to 0.61:1.5 to 1.55.
Preferably, the polyvinylpyrrolidone solution and La (NO 3 ) 3 ·6H 2 The mass ratio of O is 45-55: 2.85-2.97.
Preferably, the mixing time in the step 1) is 22-26 hours; and 2) the voltage of the electrostatic spinning is 14-18 kV, and the spinning distance is 12-16 cm.
Preferably, the calcining treatment of step 3) comprises a first calcining treatment and a second calcining treatment; in the first calcination treatment, the temperature is 350-450 ℃ and the time is 1.5-2.5 h; in the second calcination treatment, the temperature is 550-650 ℃ and the time is 0.5-1.5 h.
Preferably, the rate of temperature rise from the room temperature to the first calcination temperature and the rate of temperature rise from the first calcination temperature to the second calcination temperature are independently 4-6 ℃/min.
Preferably, the first calcination treatment is performed under a nitrogen atmosphere; the second calcination treatment is performed under an air atmosphere.
The invention also provides application of the Pd-doped perovskite oxide nanofiber in preparing biphenyl by photo-thermal catalysis or thermal catalysis Suzuki coupling reaction.
The beneficial effects of the invention include:
1) The Pd-doped perovskite oxide nanofiber La is prepared by electrostatic spinning and high-temperature calcination 0.9 Pd x Co 0.7 Mn 0.3 O 3 (x=0.1 or 0.2). La is subjected to 0.9 Pd x Co 0.7 Mn 0.3 O 3 The catalyst is used for photo-thermal catalysis Suzuki coupling reaction or thermal catalysis Suzuki coupling reaction, and the perovskite catalyst is doped with Pd element to expose more active sites of central metal, so that the Suzuki reaction process is accelerated. The results show that La 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The perovskite oxide nanofiber is easier to promote the carbon-carbon coupling activity of the Suzuki reaction, and has good circulationThe ring stability has important significance for realizing the double-carbon target.
2) The invention effectively solves the problems that Pd-containing catalyst is difficult to recycle, biphenyl products and the catalyst are difficult to separate, so that target products are polluted, the environment is polluted and the like.
Drawings
FIG. 1 is La 0.9 Pd x Co 0.7 Mn 0.3 O 3 (x is 0.1 or 0.2) a perovskite oxide nanofiber photo-thermal catalysis Suzuki coupling reaction mechanism;
FIG. 2 shows La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 Scanning electron microscope images of perovskite oxide nanofibers;
FIG. 3 shows La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 Thermally catalyzing a Suzuki coupling reaction data result by using the perovskite oxide nanofiber;
FIG. 4 shows La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The perovskite oxide nanofiber photo-thermal catalysis Suzuki coupling reaction data result;
FIG. 5 shows La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The perovskite oxide nanofiber is subjected to Suzuki coupling reaction mass spectrum data of gas chromatography-mass spectrometry analysis.
Detailed Description
The invention provides Pd-doped perovskite oxide nanofiber, which is La 0.9 Pd x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2.
The invention also provides a preparation method of the Pd-doped perovskite oxide nanofiber, which comprises the following steps:
1) Polyvinylpyrrolidone solution, la (NO 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 O is mixed to obtain spinning precursor solution;
2) Carrying out electrostatic spinning on the spinning precursor solution to obtain a polyvinylpyrrolidone nanofiber membrane;
3) Calcining the polyvinylpyrrolidone nanofiber membrane to obtain La 0.9 Pd x Co 0.7 Mn 0.3 O 3 。
In the present invention, the solvent of the polyvinylpyrrolidone solution in step 1) is preferably N, N-Dimethylformamide (DMF), and in the polyvinylpyrrolidone solution, the mass fraction of polyvinylpyrrolidone (PVP) is preferably 10 to 14%, more preferably 11 to 13%, and even more preferably 12%.
In the invention, when the Pd doped perovskite oxide nanofiber is La 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is preferably 2.85-2.97: 0.14-0.23: 0.5 to 0.61:1.5 to 1.55, more preferably 2.88 to 2.94: 0.16-0.21: 0.52-0.57: 1.51 to 1.53, more preferably 2.923:0.186:0.551:1.528;
when the Pd doped perovskite oxide nanofiber is La 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is preferably 2.85-2.97: 0.32-0.42: 0.5 to 0.61:1.5 to 1.55, more preferably 2.88 to 2.94:0.35 to 0.40: 0.52-0.57: 1.51 to 1.53, more preferably 2.923:0.373:0.551:1.528.
in the present invention, a polyvinylpyrrolidone solution and La (NO 3 ) 3 ·6H 2 The mass ratio of O is preferably 45-55: 2.85 to 2.97, more preferably 47 to 52:2.88 to 2.94, more preferably 50:2.923.
in the present invention, the mixing time in step 1) is preferably 22 to 26 hours, more preferably 23 to 25 hours, and even more preferably 24 to h; the temperature of mixing is preferably room temperature; the mixing is preferably carried out under stirring.
In the invention, the voltage of the electrostatic spinning in the step 2) is preferably 14-18 kV, more preferably 15-17 kV, and even more preferably 16 kV; the spinning distance is preferably 12 to 16 cm, more preferably 13 to 15 cm, and even more preferably 14 to cm.
In the present invention, the calcination treatment of step 3) preferably includes a first calcination treatment and a second calcination treatment; in the first calcination treatment, the temperature is preferably 350 to 450 ℃, more preferably 370 to 420 ℃, and still more preferably 390 to 400 ℃; the time is preferably 1.5-2.5 h, and more preferably 2 h; in the second calcination treatment, the temperature is preferably 550 to 650 ℃, more preferably 570 to 620 ℃, and still more preferably 590 to 600 ℃; the time is preferably 0.5 to 1.5 hours, and more preferably 1 h.
In the present invention, the rate at which the room temperature is raised to the first calcination temperature and the rate at which the first calcination temperature is raised to the second calcination temperature are independently preferably 4 to 6 ℃/min, more preferably 4.5 to 5.5 ℃/min, and even more preferably 5 ℃/min.
In the present invention, the first calcination treatment is preferably performed under a nitrogen atmosphere; the second calcination treatment is preferably performed under an air atmosphere, the process of raising the temperature of the room temperature to the first calcination temperature is preferably a nitrogen atmosphere, and the process of raising the temperature of the first calcination to the second calcination temperature is preferably an air atmosphere.
The invention also provides application of the Pd-doped perovskite oxide nanofiber in preparing biphenyl by photo-thermal catalysis or thermal catalysis Suzuki coupling reaction.
The specific method for preparing biphenyl by Pd doped perovskite oxide nanofiber photo-thermal catalysis or thermal catalysis Suzuki coupling reaction comprises the following steps: bromobenzene, phenylboronic acid, potassium carbonate and Pd doped perovskite oxide nanofiber are mixed with ethanol solution to carry out photo-thermal catalysis Suzuki coupling reaction or thermal catalysis Suzuki coupling reaction.
In the invention, the molar ratio of bromobenzene, phenylboronic acid and potassium carbonate is preferably 0.45-0.55: 0.5 to 0.6:0.45 to 0.55, more preferably 0.47 to 0.52: 0.52-0.58: 0.47 to 0.52, more preferably 0.5:0.55:0.5; the molar mass ratio of bromobenzene to Pd-doped perovskite oxide nanofiber is preferably 0.45-0.55 mmol:8 to 12 mg, more preferably 0.47 to 0.52 mmol:9 to 11 mg, more preferably 0.5 mmol:10 mg.
In the invention, the ethanol solution is an aqueous solution of absolute ethanol, and the volume ratio of the absolute ethanol to the water is preferably 1:1.
In the photo-thermal catalysis Suzuki coupling reaction, the reaction temperature is preferably 25-40 ℃, and more preferably 30-35 ℃; in the thermocatalytic Suzuki coupling reaction, the reaction temperature is preferably 75-82 ℃, and more preferably 78-80 ℃.
La 0.9 Pd x Co 0.7 Mn 0.3 O 3 The mechanism of the photo-thermal catalysis Suzuki coupling reaction of the perovskite oxide nanofiber with the x being 0.1 or 0.2 is shown in figure 1.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
To 5 g of PVP solution (DMF as solvent, 12% by mass of PVP) was added 0.2923 g of La (NO) 3 ) 3 ·6H 2 O、0.0373 g Pd(NO 3 ) 3 ·6H 2 O、0.0551 g Mn(CH 3 COO) 2 ·4H 2 O、0.1528 g Co(NO 3 ) 2 ·6H 2 O, stirring 24 h at the speed of 300r/min at room temperature to obtain a uniformly mixed spinning precursor solution. And (3) carrying out electrostatic spinning on the spinning precursor solution under the voltage of 16 kV, wherein the spinning distance is 14 cm, and obtaining the PVP nanofiber membrane. Placing PVP nanofiber membrane in a tube furnace for calcination treatment, firstly heating from room temperature to 400 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, calcining 2h at 400 ℃ under nitrogen atmosphere, then heating from 400 ℃ to 600 ℃ at a speed of 5 ℃/min under air atmosphere, and continuously maintaining 1 h at 600 ℃ under air atmosphere to obtain La 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 Perovskite oxide nanofibers.
Example 2
Pd (NO) in example 1 3 ) 3 ·6H 2 The mass of O was changed to 0.0186 and g, and La was obtained under the same conditions as in example 1 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 Perovskite oxide nanofibers.
Example 3
To 4.8 g of PVP solution (DMF solvent 13% by mass of PVP) was added 0.288 g of La (NO) 3 ) 3 ·6H 2 O、0.036 g Pd(NO 3 ) 3 ·6H 2 O、0.052 g Mn(CH 3 COO) 2 ·4H 2 O、0.151 g Co(NO 3 ) 2 ·6H 2 O, stirring 23 h at room temperature to obtain a spinning precursor solution which is uniformly mixed. And (3) carrying out electrostatic spinning on the spinning precursor solution under the voltage of 17 kV, wherein the spinning distance is 15 cm, and obtaining the PVP nanofiber membrane. The PVP nanofiber membrane is placed in a tube furnace for calcination treatment, firstly, the temperature is raised to 370 ℃ from room temperature at the speed of 4.7 ℃/min under nitrogen atmosphere, 2.5 h is calcined at 370 ℃ under nitrogen atmosphere, then the PVP nanofiber membrane is heated to 580 ℃ from 370 ℃ at the speed of 4.7 ℃/min under air atmosphere, and the La is obtained by continuously keeping 1.5 h under air atmosphere at 580 DEG C 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 Perovskite oxide nanofibers.
Example 4
To 5.2 g of PVP solution (DMF solvent 11% by mass of PVP) was added 0.295 g of La (NO) 3 ) 3 ·6H 2 O、0.017 g Pd(NO 3 ) 3 ·6H 2 O、0.058 g Mn(CH 3 COO) 2 ·4H 2 O、0.154 g Co(NO 3 ) 2 ·6H 2 O, stirring 25 and h at room temperature to obtain a spinning precursor solution which is uniformly mixed. And (3) carrying out electrostatic spinning on the spinning precursor solution under the voltage of 15 kV, wherein the spinning distance is 13 cm, and obtaining the PVP nanofiber membrane. The PVP nanofiber membrane is placed in a tube furnace for calcination treatment, firstly, the temperature is raised to 420 ℃ from room temperature at the speed of 5.2 ℃/min under the nitrogen atmosphere, and the temperature is 420 ℃ and the nitrogen is used for heatingCalcining under air at 1.5 h, heating from 150deg.C to 200deg.C at a rate of 5.2 ℃/min under air, and maintaining at 620 ℃ under air at 0.5 h to obtain La 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 Perovskite oxide nanofibers.
La 0.9 Pd x Co 0.7 Mn 0.3 O 3 The (x=0.1, 0.2) catalyst was used in the Suzuki coupling reaction to evaluate its catalytic activity, in the following steps: 0.5 mmol bromobenzene, 0.55 mmol phenylboronic acid, 0.5 mmol potassium carbonate and 10mg Pd doped perovskite oxide nanofiber (La prepared in example 1) 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 Or La prepared in example 2 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 ) Adding the mixture into an ethanol water solution (the volumes of absolute ethanol and water are 4 mL), and carrying out photo-thermal catalysis Suzuki coupling reaction or thermal catalysis Suzuki coupling reaction to prepare biphenyl, wherein the temperature of the thermal catalysis Suzuki coupling reaction is 20 ℃, 50 ℃ and 80 ℃, the photo-thermal catalysis Suzuki coupling reaction adopts a 300W xenon lamp, the light source current is 17A, a 420 nm optical filter, and the reaction temperature is 0 ℃ and 30 ℃ respectively. After the completion of the reaction, the solution was added to a separating funnel containing 6mL of ethyl acetate and 4mL of distilled water, and extraction was performed. The organic layer solution was analyzed by gas chromatography-mass spectrometry and the yield of biphenyl was calculated. The catalyst was separated by centrifugation and washed alternately with ethanol and distilled water, respectively, and then dried under vacuum at 60 ℃ and-0.1 MPa for 2h for the subsequent reaction cycle.
La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The scanning electron microscope image of the perovskite oxide nanofiber is shown in fig. 2, and as can be seen from fig. 2, the prepared catalyst is in a nanofiber shape, meanwhile, a plurality of pore structures are formed on the surface of the nanofiber, and the nanofiber is composed of perovskite nanoparticles loaded by a carbon fiber framework, so that the perovskite oxide nanofiber can be used as a catalyst in the catalytic process to provide rich active sites and a large contact area.
La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The data of the perovskite oxide nanofiber thermocatalytic Suzuki coupling reaction are shown in FIG. 3, and as can be seen from FIG. 3, la 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The perovskite oxide nanofiber is used for thermocatalytic Suzuki coupling reaction, and after heating reaction for 30 min at 80 ℃, the biphenyl yield is up to 99%; 50. after 20 min of heating reaction at the temperature, the yield of biphenyl is 66%.
La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The data result of the photo-thermal catalytic Suzuki coupling reaction of the perovskite oxide nanofiber is shown in FIG. 4, and as can be seen from FIG. 4, la 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The perovskite oxide nanofiber is used for photo-thermal catalysis Suzuki coupling reaction, and after the photo-reaction is carried out for 90 min at the temperature of 0 ℃, the biphenyl yield is 3.1%; 30. after heating and light reacting for 90 min at the temperature, the yield of biphenyl is up to 86.3 percent.
La prepared in example 1 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 The mass spectrum data of the Suzuki coupling reaction of the perovskite oxide nanofiber through gas chromatography-mass spectrometry is shown in fig. 5, and the presence of biphenyl in the product is shown in fig. 5.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A Pd-doped perovskite oxide nanofiber is characterized in that the Pd-doped perovskite oxide nanofiber is La 0.9 Pd x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2.
2. The method for preparing the Pd-doped perovskite oxide nanofiber according to claim 1, comprising the steps of:
1) Dissolving polyvinylpyrrolidoneLiquid, la (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 O is mixed to obtain spinning precursor solution;
2) Carrying out electrostatic spinning on the spinning precursor solution to obtain a polyvinylpyrrolidone nanofiber membrane;
3) Calcining the polyvinylpyrrolidone nanofiber membrane to obtain La 0.9 Pd x Co 0.7 Mn 0.3 O 3 。
3. The preparation method of the Pd-doped perovskite oxide nanofiber according to claim 2, wherein the solvent of the polyvinylpyrrolidone solution in the step 1) is N, N-dimethylformamide, and the mass fraction of polyvinylpyrrolidone in the polyvinylpyrrolidone solution is 10-14%.
4. A method of preparing a Pd doped perovskite oxide nanofiber according to claim 2 or 3, wherein when the Pd doped perovskite oxide nanofiber is La 0.9 Pd 0.1 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 2.85-2.97: 0.14-0.23: 0.5 to 0.61: 1.5-1.55;
when the Pd doped perovskite oxide nanofiber is La 0.9 Pd 0.2 Co 0.7 Mn 0.3 O 3 When La (NO) 3 ) 3 ·6H 2 O、Pd(NO 3 ) 3 ·6H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 2.85-2.97: 0.32-0.42: 0.5 to 0.61:1.5 to 1.55.
5. A Pd-doped perovskite oxide nano according to claim 4A process for producing a rice fiber characterized by comprising mixing a polyvinylpyrrolidone solution with La (NO 3 ) 3 ·6H 2 The mass ratio of O is 45-55: 2.85-2.97.
6. The method for preparing a Pd doped perovskite oxide nanofiber according to claim 5, wherein the mixing time in step 1) is 22-26 hours; and 2) the voltage of the electrostatic spinning is 14-18 kV, and the spinning distance is 12-16 cm.
7. The method of preparing a Pd-doped perovskite oxide nanofiber according to claim 5 or 6, wherein step 3) the calcination treatment comprises a first calcination treatment and a second calcination treatment; in the first calcination treatment, the temperature is 350-450 ℃ and the time is 1.5-2.5 h; in the second calcination treatment, the temperature is 550-650 ℃ and the time is 0.5-1.5 h.
8. The method for preparing the Pd doped perovskite oxide nanofiber according to claim 7, wherein the rate of temperature rise from room temperature to the first calcination temperature and the rate of temperature rise from the first calcination temperature to the second calcination temperature are independently 4-6 ℃/min.
9. The method for producing a Pd-doped perovskite oxide nanofiber according to claim 8, wherein the first calcination treatment is performed under a nitrogen atmosphere; the second calcination treatment is performed under an air atmosphere.
10. The use of the Pd-doped perovskite oxide nanofiber as defined in claim 1 in the preparation of biphenyl by photo-thermal catalysis or thermo-catalytic Suzuki coupling reaction.
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