CN111389406A - Preparation method and electrocatalysis application of perovskite electrode material - Google Patents
Preparation method and electrocatalysis application of perovskite electrode material Download PDFInfo
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- CN111389406A CN111389406A CN202010353424.1A CN202010353424A CN111389406A CN 111389406 A CN111389406 A CN 111389406A CN 202010353424 A CN202010353424 A CN 202010353424A CN 111389406 A CN111389406 A CN 111389406A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- 238000002390 rotary evaporation Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000411 inducer Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- NWXMGUDVXFXRIG-WESIUVDSSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O NWXMGUDVXFXRIG-WESIUVDSSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 150000008365 aromatic ketones Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002248 LaBO3 Inorganic materials 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 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
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J23/83—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 rare earths or actinides
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Abstract
The invention discloses a preparation method of a perovskite electrode material and electrocatalysis application thereof, which is characterized in that L a (NO) is added3)3·6H2O is lanthanum source and Fe (NO)3)3·9H2Iron O source, Co (NO)3)2·6H2Source of O cobalt or Ni (NO)3)2·6H2Mixing an O nickel source, taking citric acid monohydrate as a complexing agent, obtaining a perovskite electrode material by adopting a sol-gel method, taking the perovskite electrode material as acetophenone, carrying out asymmetric electro-carboxylation reaction to synthesize a cathode material with optical activity 2-hydroxy-2-phenylpropionic acid, and carrying out electro-carboxylation reaction under normal pressure saturated carbon dioxide. Compared with the prior art, the invention has the advantages of simple preparation of electrode materials, low cost and good catalytic activity in the electro-carboxylation reaction of acetophenone, and has very good application prospectThe electrocatalytic material can effectively utilize greenhouse-effect gas carbon dioxide, and simultaneously realizes the conversion of acetophenone and the effective synthesis of chiral substances.
Description
Technical Field
The invention relates to the technical field of electrochemical reduction, in particular to L aBO3(B = Fe/Co/Ni) perovskite electrode material and its preparation method and electrocatalysis application in acetophenone asymmetric electro-carboxylation reaction.
Background
The asymmetric synthesis of important pharmaceutical intermediate carboxylic acids by using electrochemical fixation of carbon dioxide and aromatic ketones is a valuable direction for research using the method.J.X. L u and the like reports that carboxylation products produced by using alkaloids as inducers and using stainless steel (Ss) or aromatic ketones using Ag, Ni and Ti as cathodes have corresponding optical activity and carboxylation activity in K.Zhang, H.Wang, S.F.ZHao, D.F.Niu, J.X. L uJ. electroanal. chem. 2009, 630, 35-41 and B. L. Chen, Z.Y. L u, electrochim. Acta, 2014, 116, 475-483.
The perovskite material has excellent electron-ion mixed conductivity, is a functional material with wide application, has a stable skeleton structure, cations in the skeleton structure have certain substitutability, oxygen holes can be generated or defects can be formed by valence change of transition metal oxides, the absorption and desorption properties of oxygen can be changed, the catalytic performance is improved, and CO have high catalytic performance2An active catalyst for activation. Recent applications of perovskite-type catalysts in electrochemistry include: CO 22Reducing into small molecular compounds (M, Schwartz, R) such as methanol, formic acid, ethanol and the like.L, Cook, V.M. Kehae, R.C. MacDuff, J.Patel, and A.F. Sammels, J.electrochem. Soc. 1993, 140, 614-618), OER and ORR (Y. L. Zhu, W.ZHou, J.Y, Y.B. Chen, M. L. L iu, and Z.P. Shao, chem. Mater. 2016, 28, 1691-1697), etc., and exhibit good electrocatalytic activity and stability.
In the prior art, a flat electrode is used as a cathode material in the asymmetric electro-carboxylation reaction of aromatic ketone, and the problems of low optical purity of a product, small specific surface area of the flat electrode, relatively few active sites and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of a perovskite electrode material and an electrocatalysis application thereof aiming at the defects of the prior art, wherein L a (NO) is prepared by adopting a sol-gel method3)3·6H2O is lanthanum source and Fe (NO)3)3·9H2O is iron source, Co (NO)3)2·6H2O is a cobalt source or Ni (NO)3)2·6H2O is taken as a nickel source to be mixed, citric acid monohydrate is taken as a complexing agent to obtain L aBO3(B = Fe/Co/Ni) perovskite electrode material is used as acetophenone asymmetric electro-carboxylation reaction to synthesize a cathode material with optically active 2-hydroxy-2-phenylpropionic acid, and the electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, the electro-catalysis material has simple preparation method and low cost, shows good catalytic activity in the electro-carboxylation reaction of acetophenone, is an electro-catalysis material with wide application prospect, has mild reaction conditions and convenient operation, and particularly uses rich C1 resource CO2As one of the raw materials, the method changes waste into valuable, does not pollute the environment, realizes the conversion of acetophenone and the effective synthesis of chiral substances, is an important chiral drug intermediate, and is a process route with industrial synthesis value.
The technical scheme for realizing the purpose of the invention is that L aBO3The preparation method of (B = Fe/Co/Ni) perovskite electrode material is characterized by comprising L a (NO)3)3·6H2O is lanthanum source, Fe (NO)3)3·9H2Is iron source, Co (NO)3)2·6H2O is a cobalt source or Ni (NO)3)2·6H2O is a nickel source, citric acid monohydrate is a complexing agent, a sol-gel method is adopted to obtain the perovskite electrode material, and the preparation method specifically comprises the following steps:
a. preparation of the precursor
L a (NO) with the metal molar ratio of 1: 0.8-1.5 is weighed3)3·6H2O and Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2Dissolving O in 10-50 m L distilled water, uniformly mixing, adding citric acid monohydrate in an amount which is 0.8-2.0 times of the molar ratio of the total metal ions, then carrying out rotary evaporation on the mixed solution in a water bath at the temperature of 70-85 ℃ to remove the solvent to obtain wet gel, and then drying at the temperature of 100-180 ℃ for 12-24 hours to obtain fluffy powder as a precursor.
b、LaBO3Preparation of (B = Fe/Co/Ni) perovskite electrode material
And grinding the prepared precursor, and roasting in a muffle furnace at 500-1100 ℃ for 4-8 h to obtain the perovskite electrode material.
L aBO3The electro-catalysis application of (B = Fe/Co/Ni) perovskite electrode material is characterized in that L aBO is added3(B = Fe/Co/Ni) perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell, a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is an inducer, n-butyl alcohol, ethanol or isopropanol is a proton source, electro-carboxylation reaction is carried out under normal pressure saturated carbon dioxide by constant current electrolysis, the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, and electro-catalysis is carried out according to the following steps:
a. preparation of the electrolyte
Mixing acetophenone with tetra-n-butylammonium iodide and CoⅡMixing (R, R) (salen), a proton source and N, N-dimethylformamide into an electrolyte according to a molar ratio of 0.5-2: 1-5: 0.01-0.1: 0.1-1: 258, and then putting the electrolyte into a one-chamber type electrolytic cell.
b. Electro-carboxylation reaction
Introducing carbon dioxide into the electrolytic cell under normal pressure until the carbon dioxide is saturated, and then introducing the carbon dioxide into the electrolytic cell at the concentration of 2-7 mA cm-2And carrying out asymmetric electro-carboxylation reaction on the acetophenone at constant current density, wherein the pressure of carbon dioxide is 1 atm, the electrolysis temperature is 5-55 ℃, and the energization amount of each mole of acetophenone is 0.5-3F, wherein F is a Faraday constant.
c. Rotary steaming machine
And (2) carrying out reduced pressure rotary evaporation on the electrolyzed liquid at the temperature of 70-85 ℃, removing the solvent of N, N-dimethylformamide, adding hydrochloric acid with the concentration of 1-2 mol/L for acidification until the solids in the rotary evaporation liquid are completely dissolved, extracting with 20 m L analytically pure anhydrous ethyl ether for three times each time, combining organic layers in the extract liquid, dehydrating and drying for 1 hour by using anhydrous magnesium sulfate, filtering, and carrying out rotary evaporation on the filtrate at the temperature of 20-25 ℃ to remove the ethyl ether to obtain the product of the 2-hydroxy-2-phenylpropionic acid with optical activity.
The citric acid monohydrate accounts for 0.8-1.6 times, preferably 1.2 times of the molar ratio of the total metal ions.
The roasting temperature is 500-1100 ℃, and preferably 700 ℃.
Compared with the prior art, the invention has the advantages of simple preparation method of the catalyst, low cost, good catalytic activity in the electro-carboxylation reaction of acetophenone, mild reaction condition, convenient operation and abundant C1 resource CO, and is an electro-catalytic material with wide application prospect2As one of the raw materials, the method changes waste into valuable, does not pollute the environment, realizes the conversion of acetophenone and the effective synthesis of chiral substances, is an important chiral drug intermediate, and is a process route with industrial synthesis value.
Drawings
FIG. 1 is a perovskite XRD pattern prepared for each example;
FIG. 2 is L aFeO prepared in example 13500 perovskite SEM images;
FIG. 3 is L aFeO prepared in example 23700 perovskite SEM images;
FIG. 4 is L aCoO prepared in example 33500 perovskite SEM images;
FIG. 5 is L aCoO prepared in example 43700 perovskite SEM picture;
FIG. 6 is L aNiO prepared in example 53500 perovskite SEM images;
FIG. 7 is L aNiO prepared in example 63700 perovskite SEM images.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
a. Preparation of the precursor
1.0825 g (0.0025 mol) L a (NO) are weighed out3)3·6H2O and 0.4496 g (0.0025 mol) Fe (NO)3)3·9H2Dissolving O in 50 m L distilled water to form transparent aqueous solution, stirring for 10 min, adding 1.2608 g (0.006 mol) citric acid monohydrate, stirring for 30 min, rotationally evaporating the solvent in a water bath at 85 ℃, drying the obtained wet gel at 180 ℃ for 12 h, and obtaining fluffy powder as a precursor.
b. Preparation of perovskite electrode material
Grinding the prepared precursor, placing the ground precursor into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible at the temperature of 500 ℃ for 5 hours to obtain L aFeO3Perovskite electrode material (labeled L aFeO)3500）。
Referring to FIG. 1, the above product was characterized by XRD (L aFeO)3Curve 500), the electrode material conforms to the characteristic diffraction peaks of JCPDs cadno. 75-0541 perovskite, indicating that the perovskite material is synthesized, but the perovskite characteristic peaks are relatively weak.
Referring to FIG. 2, the above product was characterized by scanning electron microscopy and firing temperature versus the resulting perovskite L aFeO3Has a great influence on the morphology of the particles. Wherein, when the roasting temperature is 500 ℃, perovskite materials are stacked together to form a block structure.
Example 2
a. Preparation of the precursor
Same as example 1, step a.
b. Preparation of perovskite electrode material
Grinding the precursor prepared aboveThen placing the mixture into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible for 5 hours at the temperature of 700 ℃ to obtain a product of L aFeO3Perovskite electrode material (labeled L aFeO)3700）。
Referring to FIG. 1, the above product was characterized by XRD (L aFeO)3700 curve), the electrode material conforms to the characteristic diffraction peak of JCPDs cadno. 75-0541 perovskite, and indicates that the perovskite material with better crystal form is formed.
Referring to FIG. 3, the above product was characterized by scanning electron microscopy as perovskite L aFeO3The particles 700 are uniformly dispersed.
Example 3
a. Preparation of the precursor
1.0825 g (0.0025 mol) L a (NO) are weighed out3)3·6H2O and 1.0000 g (0.0025 mol) Co (NO)3)2·6H2Dissolving O in 50 m L distilled water to form transparent aqueous solution, stirring for 10 min, adding 1.2608 g (0.006 mol) citric acid monohydrate, stirring for 30 min, rotationally evaporating the solvent in a water bath at 85 ℃, drying the obtained wet gel at 180 ℃ for 12 h to obtain fluffy powder as a precursor.
b. Preparation of perovskite electrode material
Grinding the precursor, placing the ground precursor into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible at the temperature of 500 ℃ for 5 hours to obtain L aCoO3To perovskite electrode material (labeled L aCoO)3500）。
Referring to FIG. 1, the above product was characterized by XRD (L aCoO)3Curve 500), the electrode material has no characteristic diffraction peak of perovskite, and indicates that the perovskite material is not synthesized and has more impurities.
Referring to FIG. 4, the above product was characterized by scanning electron microscopy and firing temperature versus perovskite L aCoO obtained3Wherein, when the roasting temperature is 500 ℃, L aCoO 3500 of material are stacked together to form a block structure.
Example 4
a. Preparation of the precursor
The same as in step a of example 3.
b. Preparation of perovskite electrode material
Grinding the precursor, placing the ground precursor into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible at 700 ℃ for 5 hours to obtain L aCoO3Perovskite electrode material (labeled L aCoO)3700）。
Referring to FIG. 1, the above product was characterized by XRD (L aCoO)3700 curve), the electrode material conforms to the characteristic diffraction peaks of JCPDs cadno. 84-0848 perovskite, indicating that the perovskite material was synthesized.
With reference to FIG. 5, the above product was characterized by scanning electron microscopy, perovskite L aCoO3The particles 700 are uniformly dispersed.
Example 5
a. Preparation of the precursor
1.0825 g (0.0025 mol) L a (NO) are weighed out3)3·6H2O and 0.7270 g (0.0025 mol) Ni (NO)3)2·6H2Dissolving O in 50 m L distilled water to form transparent aqueous solution, stirring for 10 min, adding 1.2608 g (0.006 mol) citric acid monohydrate, stirring for 30 min, rotationally evaporating the solvent in a water bath at 85 ℃, drying the obtained wet gel at 180 ℃ for 12 h, and obtaining fluffy powder as a precursor.
b. Preparation of perovskite electrode material
Grinding the prepared precursor, placing the ground precursor into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible for 5 hours at the temperature of 500 ℃ to obtain L aNiO3Perovskite electrode material (labeled L aNiO)3500）。
Referring to FIG. 1, the above product was characterized by XRD (L aNiO)3Curve 500), the electrode material has no characteristic diffraction peak of perovskite, and indicates that the perovskite material is not synthesized and has more impurities.
Referring to FIG. 6, the above product was characterized by scanning electron microscopy and firing temperature versus perovskite L aNiO obtained3Wherein, when the roasting temperature is 500 ℃, L aNiO is used3500 of material are stacked together to form a block structure.
Example 6
a. Preparation of the precursor
Same as example 5, step a.
b. Perovskite L aNiO 3700 preparation of electrode Material
Grinding the prepared precursor, placing the ground precursor into a crucible, covering the crucible, placing the crucible into a muffle furnace, and roasting the crucible for 5 hours at the temperature of 700 ℃ to obtain a product of L aNiO3Perovskite electrode material (labeled L aNiO)3700）。
Referring to FIG. 1, the above product was characterized by XRD (L aNiO)3700 curve) which conforms to the characteristic diffraction peaks of JCPDs cadno. 88-0633 perovskites, indicating that perovskite materials were synthesized.
Referring to FIG. 7, the above product was characterized by scanning electron microscopy, perovskite L aNiO3The particles 700 are uniformly dispersed.
Example 7
L aFeO prepared in example 13500 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butanol is used as a proton source (hydrogen source), electro-carboxylation reaction is carried out under normal pressure saturated carbon dioxide by constant current electrolysis, and 2-hydroxy-2-phenylpropionic acid with optical activity is obtained after rotary evaporation, extraction and purification of reaction liquid, and the specific application is carried out according to the following steps:
a. preparation of the electrolyte
Mu. L (0.001 mol) acetophenone was mixed with 20 m L (0.258 mol) N, N-dimethylformamide, 0.7387 g (0.002 mol) tetrabutylammonium iodide, 45 mu L (0.0005 mol) N-butanol and 0.0302 g (0.00005 mol) Co II- (R, R) (salen) to form an electrolyte solution, which was then placed in the perovskite L aFeO 3500 electrode material is a cathode and a magnesium rod is an anode; the acetophenone, the N, N-dimethylformamide, the tetra-N-butylammonium iodide and the chiral CoⅡThe (R, R) (salen) inducer and the n-butanol are analytically pure, wherein the acetophenone is used as a substrate, the tetra-n-butylammonium iodide is used as a supporting electrolyte, and the chiral Co isⅡ- (R, R) (salen) is an inducer, N-butanol is a proton source, N,the N-dimethylformamide is a dried solvent of a 4 Å -grade molecular sieve.
b. Electro-carboxylation reaction
Introducing carbon dioxide into the electrolytic cell under normal pressure until the carbon dioxide is saturated, and then introducing the carbon dioxide into the electrolytic cell at the concentration of 5 mA cm-2Asymmetric electro-carboxylation reaction is carried out at constant current density, carbon dioxide is introduced until the electrolysis is finished, the pressure of the carbon dioxide is 1 atm, the electrolysis temperature is 25 ℃, and the electricity supply amount is 193 ℃ (the electricity supply amount per mol of acetophenone is 2F, and F is a Faraday constant).
c. Rotary steaming machine
And (2) carrying out reduced pressure rotary evaporation on the electrolyzed liquid at the temperature of 80 ℃, removing the solvent of N, N-dimethylformamide, adding hydrochloric acid with the concentration of 2 mol/L for acidification until the solid in the rotary evaporation liquid is completely dissolved, extracting with 20 m L analytically pure anhydrous ether for three times each time, combining organic layers in the extract liquid, dehydrating and drying for 1 hour by using anhydrous magnesium sulfate, filtering, and carrying out rotary evaporation on the filtrate at the temperature of 22 ℃ to remove ether to obtain the product of 2-hydroxy-2-phenylpropionic acid with optical activity, wherein the rotary evaporation pressure is 0.1 MPa.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 27%, the ee value is 72%, and the detection conditions comprise that n-hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm, and the flow rate is 0.5 ml/min.
Example 8
L aFeO prepared in example 23700 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, and the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, which is specifically applied according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electro-carboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of step c of example 7.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 32 percent, the ee value is 86 percent, and the detection conditions comprise normal hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm and the flow rate is 0.5 ml/min.
Example 9
L aCoO prepared in example 33500 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, and the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, which is specifically applied according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electro-carboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of step c of example 7.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 25 percent, the ee value is 75 percent, and the detection conditions comprise normal hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm and the flow rate is 0.5 ml/min.
Example 10
L aCoO prepared in example 43700 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, and the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, which is specifically applied according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electro-carboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of step c of example 7.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 38%, the ee value is 85%, and the detection conditions are that n-hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm, and the flow rate is 0.5 ml/min.
Example 11
L aNiO prepared in example 53500 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, and the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, which is specifically applied according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electro-carboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of step c of example 7.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 35 percent, the ee value is 86 percent, and the detection conditions comprise normal hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm and the flow rate is 0.5 ml/min.
Example 12
L aNiO prepared in example 63700 perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡ- (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, electro-carboxylation reaction is carried out by constant current electrolysis under normal pressure saturated carbon dioxide, and the reaction liquid is subjected to rotary evaporation, extraction and purification to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, which is specifically applied according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electro-carboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of step c of example 7.
The product is detected by high performance liquid chromatography (HP L C) and a chiral AD-H column, and the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 40%, the ee value is 87%, and the detection conditions are that n-hexane, isopropanol, trifluoroacetic acid = 80: 20: 1, the wavelength is 235 nm, and the flow rate is 0.5 ml/min.
As can be seen from the above examples, the perovskite L aFeO3、LaCoO3And L aNiO3The yield of the electrode material for preparing the optically active 2-hydroxy-2-phenylpropionic acid by asymmetrically electro-carboxylating acetophenone is respectively as high as 32%, 38% and 40%, and the ee value is respectively as high as 86%, 85% and 87%, which is far higher than the asymmetric electro-carboxylation effect of the stainless steel electrode for acetophenone, wherein the yield is 25% and the ee value is 30%. The perovskite electrocatalyst exhibits better electrocatalytic activity than the conventional stainless steel sheet electrode. The perovskite material is used for synthesizing important chiral drug intermediate carboxylic acid by asymmetric electro-carboxylation aromatic ketone, so that the application range of the perovskite material is widened.
The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.
Claims (4)
1. A preparation method of perovskite electrode material is characterized in that L a (NO) is prepared by adopting a sol-gel method3)3·6H2O is lanthanum source and Fe (NO)3)3·9H2O is iron source, Co (NO)3)2·6H2O is a cobalt source or Ni (NO)3)2·6H2O as nickel source and citric acid monohydrate as complexing agent to prepare L aBO3The perovskite electrode material is specifically prepared by the following steps:
a. preparation of the precursor
L a (NO)3)3·6H2O and Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2Dissolving O in L distilled water with the metal ion molar ratio of 1: 0.8-1.5 to 10-50 m, uniformly mixing, adding citric acid monohydrate in an amount which is 0.8-2.0 times of the total metal ion molar ratio, then rotationally evaporating the solvent from the mixed solution at the temperature of 70-85 ℃, drying the obtained wet gel at the temperature of 100-180 ℃ for 12-24 hours, and preparing fluffy powder as a precursor;
b. preparation of perovskite electrode material
Grinding the prepared precursor, and roasting at 500-1100 ℃ for 4-8 h to obtain L aBO3A perovskite electrode material, wherein B is Fe, Co or Ni.
2. The process for the preparation of a perovskite electrode material as claimed in claim 1, characterized in that the amount of citric acid monohydrate is 0.8 to 2.0 times, preferably 1.2 times the total metal ions.
3. The process for preparing a perovskite electrode material as claimed in claim 1, wherein the firing temperature is 500 to 1100 ℃, preferably 700 ℃.
4. Electrocatalytic use of a perovskite electrode material prepared by a process of preparing a perovskite electrode material according to claim 1, characterized in that L aBO is added3Perovskite electrode material is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed into electrolyte, and Co is usedⅡThe preparation method comprises the following steps of (1) - (R, R) as an inducer, n-butanol, ethanol or isopropanol as a proton source, carrying out electro-carboxylation reaction by constant current electrolysis under normal pressure saturated carbon dioxide, and carrying out rotary evaporation, extraction and purification on reaction liquid to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, wherein the electro-catalysis application specifically comprises the following steps:
a. preparation of the electrolyte
Mixing acetophenone with tetra-n-butylammonium iodide and CoⅡElectrolyte prepared by (R, R), a proton source and N, N-dimethylformamide according to the molar ratio of 0.5-2: 1-5: 0.01-0.1: 0.1-1: 258 is put into a one-chamber type electrolytic cell;
b. electro-carboxylation reaction
Introducing carbon dioxide into an electrolytic cell under normal pressure until the carbon dioxide is saturated, and then introducing the carbon dioxide into the electrolytic cell at the concentration of 2-7 mA cm-2Carrying out asymmetric electro-carboxylation reaction on acetophenone at constant current density, wherein the pressure of carbon dioxide is 1 atm, the electrolysis temperature is 5-55 ℃, and the electrification amount is 0.5-3F per mole of acetophenone, wherein F is a Faraday constant;
c. rotary steaming machine
And (3) carrying out reduced pressure rotary evaporation on the electrolyzed liquid at the temperature of 70-85 ℃, removing the solvent of N, N-dimethylformamide, adding hydrochloric acid with the concentration of 1-2 mol/L for acidification until the solid in the rotary evaporation liquid is completely dissolved, extracting with 20 m L analytically pure anhydrous ethyl ether for three times each time, combining organic layers in the extract liquid, dehydrating and drying for 1 hour by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation on the filtrate at the temperature of 20-25 ℃, and removing the ethyl ether to obtain the product, namely the 2-hydroxy-2-phenylpropionic acid with optical activity.
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