CN111389406B - Preparation method and electrocatalysis application of perovskite electrode material - Google Patents
Preparation method and electrocatalysis application of perovskite electrode material Download PDFInfo
- Publication number
- CN111389406B CN111389406B CN202010353424.1A CN202010353424A CN111389406B CN 111389406 B CN111389406 B CN 111389406B CN 202010353424 A CN202010353424 A CN 202010353424A CN 111389406 B CN111389406 B CN 111389406B
- Authority
- CN
- China
- Prior art keywords
- electrode material
- perovskite
- electro
- acetophenone
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 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 41
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 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 10
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 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 32
- 239000000047 product Substances 0.000 claims description 29
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- 238000002390 rotary evaporation Methods 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 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 claims description 13
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 13
- 239000000411 inducer Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 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
- 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
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 241000877463 Lanio Species 0.000 description 15
- 229910017771 LaFeO Inorganic materials 0.000 description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- 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
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000001704 evaporation Methods 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
- 150000008365 aromatic ketones Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- -1 aromatic ketone compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate 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
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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 perovskite electrode material and electrocatalysis application thereof, which is characterized in that La (NO) is added 3 ) 3 ·6H 2 O is lanthanum source and Fe (NO) 3 ) 3 ·9H 2 Iron O source, co (NO) 3 ) 2 ·6H 2 Source of O cobalt or Ni (NO) 3 ) 2 ·6H 2 Mixing 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 the acetophenone, is an electro-catalytic material with wide application prospect, can effectively utilize greenhouse effect gas carbon dioxide, and simultaneously realizes the conversion of the acetophenone and the effective synthesis of chiral substances.
Description
Technical Field
The invention relates to the technical field of electrochemical reduction, in particular to LaBO 3 (B = Fe/Co/Ni) perovskite electrode material and its electrocatalysis application in acetophenone asymmetric electro-carboxylation reaction.
Background
Carbon dioxide is a main member of global greenhouse effect, and activation and utilization of carbon dioxide not only can control greenhouse gas emission and slow down environmental pollution, but also can synthesize important chemical products by utilizing cheap and rich Cl resources. The asymmetric synthesis of important drug intermediate carboxylic acid by electrochemical fixation of carbon dioxide and aromatic ketone compounds is a valuable direction for research by applying the method. Asymmetric electro-carboxylation with alkaloids as inducers and aromatic ketones as substrates with stainless steel (Ss) or Ag, ni and Ti as cathodes to give optically active corresponding carboxylated products has been reported by j.x. Lu et al in k. Zhang, h.wang, s.f. Zhao, d.f. Niu, j.x. Lu. Electroananal. Chem. 2009, 630, 35-41 and b.l. Chen, z.y. Tu, h.zhu, w.w. Sun, h.wang, j.x. Lu, 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 replaceability, and oxygen holes can be generated or defects can be formed by the valence change of transition metal oxides, so that the adsorption and desorption properties of oxygen can be changed, the catalytic performance is improved, and CO are used as catalyst 2 An active catalyst for activation. Recent applications of perovskite-type catalysts in electrochemistry include: CO 2 2 Reduced to small molecule compounds such as methanol, formic acid and ethanol (M. Schwartz, R.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. Liu, 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 perovskite electrode material preparation method and electrocatalysis application thereof aiming at the defects of the prior art, and La (NO) is prepared by adopting a sol-gel method 3 ) 3 ·6H 2 O is lanthanum source and Fe (NO) 3 ) 3 ·9H 2 O isIron source, co (NO) 3 ) 2 ·6H 2 O is a cobalt source or Ni (NO) 3 ) 2 ·6H 2 Mixing O as nickel source and citric acid monohydrate as complexing agent to obtain LaBO 3 (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 abundant C1 resource CO 2 As 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 as follows: laBO 3 The preparation method of (B = Fe/Co/Ni) perovskite electrode material is characterized in that La (NO) is used 3 ) 3 ·6H 2 O is lanthanum source, fe (NO) 3 ) 3 ·9H 2 Is iron source, co (NO) 3 ) 2 ·6H 2 O is a cobalt source or Ni (NO) 3 ) 2 ·6H 2 O 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
Weighing La (NO) with a metal molar ratio of 1 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O or Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 10-50 mL of distilled water, mixing uniformly, adding citric acid monohydrate in an amount which is 0.8-2.0 times of the molar ratio of the total metal ions, then rotationally evaporating the solvent from the mixed solution in a water bath at the temperature of 70-85 ℃ to obtain wet gel, and drying at the temperature of 100-180 ℃ for 12-24 hours to obtain fluffy powder serving as a precursor.
b、LaBO 3 (B=Fe/Preparation of Co/Ni) perovskite electrode material
And grinding the prepared precursor, and roasting in a muffle furnace at the temperature of 500-1100 ℃ for 4-8 h to obtain the perovskite electrode material.
LaBO 3 The electro-catalysis application of (B = Fe/Co/Ni) perovskite electrode material is characterized in that LaBO is used 3 (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 used Ⅱ - (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 Co Ⅱ - (R, R) (salen), a proton source and N, N-dimethylformamide are mixed into an electrolyte according to a molar ratio of 0.5 to 2.
b. Electrocarboxylation reaction
Introducing carbon dioxide into the electrolytic cell under normal pressure until the electrolytic cell is saturated, and then introducing carbon dioxide into the electrolytic cell at a flow rate of 2 to 7 mA cm -2 And 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 the 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 solid in the rotary evaporation liquid is completely dissolved, extracting with 20 mL of analytically pure anhydrous ether for three times each time, combining organic layers in the extraction 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 ether to obtain the product, namely the 2-hydroxy-2-phenylpropionic acid with optical activity.
The citric acid monohydrate accounts for 0.8 to 1.6 times, preferably 1.2 times of the molar ratio of the total metal ions.
The baking temperature is 500 to 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 prospect 2 As 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 shows LaFeO prepared in example 1 3 500 perovskite SEM images;
FIG. 3 shows LaFeO prepared in example 2 3 700 perovskite SEM images;
FIG. 4 shows LaCoO prepared in example 3 3 500 perovskite SEM images;
FIG. 5 shows LaCoO prepared in example 4 3 700 perovskite SEM images;
FIG. 6 shows LaNiO prepared in example 5 3 500 perovskite SEM images;
FIG. 7 shows LaNiO prepared in example 6 3 700 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) La (NO) is weighed out 3 ) 3 ·6H 2 O and 0.4496 g (0.0025 mol) Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 50 mL of distilled water to form a transparent aqueous solution, stirring for 10 min, adding 1.2608 g (0.006 mol) of citric acid monohydrate, stirring for 30 min, and rotary evaporating the solvent in a water bath at 85 deg.C to obtain a wet gel at 180 deg.CDrying for 12 h to obtain fluffy powder as 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 a product LaFeO 3 Perovskite electrode material (labeled as LaFeO) 3 500）。
Referring to FIG. 1, the above product was characterized by XRD (LaFeO) 3 Curve 500), the electrode material conforms to the characteristic diffraction peak of JCPDs card No.75-0541 perovskite, which indicates that the perovskite material is synthesized, but the characteristic peak of the perovskite is relatively weak.
Referring to the attached figure 2, the product is characterized by a scanning electron microscope, and the roasting temperature is measured on the obtained perovskite LaFeO 3 Has a great influence on the morphology of the steel. Wherein, when the roasting temperature is 500 ℃, the perovskite materials are piled 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, 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 a product LaFeO 3 Perovskite electrode material (labeled as LaFeO) 3 700）。
Referring to FIG. 1, the above product was characterized by XRD (LaFeO) 3 700 curve), the electrode material conforms to the characteristic diffraction peak of JCPDs card No.75-0541 perovskite, which indicates that the perovskite material with better crystal form is formed.
Referring to the attached figure 3, the perovskite LaFeO is characterized by a scanning electron microscope 3 The particles 700 are uniformly dispersed.
Example 3
a. Preparation of the precursor
1.0825 g (0.0025 mol) La (NO) is weighed out 3 ) 3 ·6H 2 O and 1.0000 g (0.0025 mol) Co (NO) 3 ) 2 ·6H 2 Dissolving O in 50 mL of distilled water to form a transparent aqueous solution, stirringStirring for 10 min, adding 1.2608 g (0.006 mol) citric acid monohydrate, stirring for 30 min, rotary evaporating solvent in water bath at 85 deg.C to obtain wet gel, and drying at 180 deg.C for 12 hr to obtain fluffy powder as 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 a product LaCoO 3 To perovskite electrode materials (labelled as LaCoO) 3 500）。
With reference to FIG. 1, the above product was characterised by XRD (LaCoO) 3 Curve 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 the attached figure 4, the product is characterized by a scanning electron microscope, and the roasting temperature is opposite to the obtained perovskite LaCoO 3 Has a great influence on the morphology of the steel. Wherein, when the roasting temperature is 500 ℃, laCoO 3 500 of material are stacked together to form a block structure.
Example 4
a. Preparation of the precursor
Same as example 3, step a.
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 a product LaCoO 3 Perovskite electrode material (labeled as LaCoO) 3 700）。
Referring to FIG. 1, the above product was characterized by XRD (LaCoO) 3 700 curve), the electrode material conforms to the characteristic diffraction peaks of JCPDs card No.84-0848 perovskite, indicating that the perovskite material was synthesized.
With reference to FIG. 5, the above product was characterized by scanning electron microscopy and perovskite LaCoO 3 The particles 700 are uniformly dispersed.
Example 5
a. Preparation of the precursor
1.0825 g (0.0025 mol) La (NO) is weighed out 3 ) 3 ·6H 2 O and 0.7270 g (0).0025 mol）Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50 mL of distilled water to form a transparent aqueous solution, stirring for 10 min, adding 1.2608 g (0.006 mol) of citric acid monohydrate, stirring for 30 min, rotationally evaporating the solvent in a water bath at the temperature of 85 ℃, and drying the obtained wet gel at the temperature of 180 ℃ for 12 h to obtain fluffy powder serving 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 a LaNiO product 3 Perovskite electrode material (labeled as LaNiO) 3 500）。
Referring to FIG. 1, the above product was characterized by XRD (LaNiO) 3 Curve 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 the attached figure 6, the product is characterized by a scanning electron microscope, and the roasting temperature is opposite to the obtained perovskite LaNiO 3 Has a great influence on the morphology of the particles. Wherein, when the roasting temperature is 500 ℃, laNiO 3 500 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 LaNiO 3 700 preparation of 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 a product LaNiO 3 Perovskite electrode material (labeled as LaNiO) 3 700）。
Referring to FIG. 1, the above product was characterized by XRD (LaNiO) 3 700 curve) which conforms to the characteristic diffraction peak of JCPDs card No.88-0633 perovskite, indicating that a perovskite material was synthesized.
With reference to the attached figure 7, the perovskite LaNiO is characterized by a scanning electron microscope 3 The particles 700 are uniformly dispersed.
Example 7
Prepared from example 1Prepared LaFeO 3 500 perovskite electrode material is used as a cathode of a one-chamber electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed to form electrolyte, and Co is used Ⅱ - (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) of acetophenone was mixed with 20 mL (0.258 mol) of N, N-dimethylformamide, 0.7387 g (0.002 mol) of tetrabutylammonium iodide, 45. Mu.L (0.0005 mol) of N-butanol and 0.0302 g (0.00005 mol) of Co II- (R, R) (salen) to prepare an electrolyte solution, which was then placed in the perovskite LaFeO 3 500 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 Co Ⅱ The (R, R) (salen) inducer and the n-butyl alcohol are analytically pure, wherein the acetophenone is taken as a substrate, the tetra-n-butylammonium iodide is taken as a supporting electrolyte, and the chiral Co is Ⅱ - (R, R) (salen) is an inducer, N-butanol is a proton source, and N, N-dimethylformamide is a solvent obtained after drying a 4A 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 -2 Asymmetric 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 193C (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 mL of analytically pure anhydrous ether for three times each time, combining organic layers in the extract liquor, dehydrating and drying for 1 h 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 (HPLC) and a chiral AD-H column, and the 2-hydroxy-2-phenylpropionic acid with optical activity is mainly in R configuration, the yield is 27 percent, and the ee value is 72 percent. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
Example 8
LaFeO prepared in example 2 3 700 perovskite electrode material is used as a cathode of a one-chamber electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed to form electrolyte, and Co is used Ⅱ - (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. Electrocarboxylation 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.
Detecting the product by High Performance Liquid Chromatography (HPLC) and chiral AD-H column, and determining that the optically active 2-hydroxy-2-phenylpropionic acid has R configuration as main component, yield of 32% and ee value of 86%. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
Example 9
LaCoO prepared in example 3 3 500 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 used Ⅱ - (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, and the mixture is saturated at normal pressurePerforming electro-carboxylation reaction under the condition of carbon dioxide by constant current electrolysis, and performing rotary evaporation, extraction and purification on reaction liquid to obtain 2-hydroxy-2-phenylpropionic acid with optical activity, wherein the specific application comprises 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.
Detecting the product by High Performance Liquid Chromatography (HPLC) and chiral AD-H column, and determining that the optically active 2-hydroxy-2-phenylpropionic acid is mainly in R configuration, the yield is 25%, and the ee value is 75%. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
Example 10
LaCoO prepared in example 4 3 700 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 used Ⅱ - (R, R) (salen) is used as an inducer, n-butyl alcohol is used as a hydrogen source, the 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 the 2-hydroxy-2-phenylpropionic acid with optical activity, and the specific application is carried out according to the following steps:
a. preparation of the electrolyte
Same as example 7, step a.
b. Electrocarboxylation reaction
Same as example 7, step b.
c. Rotary steaming machine
The rotary evaporation process is the same as that of example 7, step c.
Detecting the product by High Performance Liquid Chromatography (HPLC) and chiral AD-H column, wherein the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 38%, and the ee value is 85%. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
Example 11
LaNiO prepared in example 5 3 500 perovskite electrode material is used as a cathode of a one-chamber electrolytic cell and a magnesium rod is used as an anode, acetophenone, N-dimethylformamide and tetra-N-butylammonium iodide are mixed to form electrolyte, and Co is used Ⅱ - (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.
Detecting the product by High Performance Liquid Chromatography (HPLC) and chiral AD-H column, wherein the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 35%, and the ee value is 86%. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
Example 12
LaNiO prepared in example 6 3 700 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 used Ⅱ - (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.
Detecting the product by High Performance Liquid Chromatography (HPLC) and chiral AD-H column, and determining that the optically active 2-hydroxy-2-phenylpropionic acid is mainly R-shaped, the yield is 40%, and the ee value is 87%. The detection conditions are mobile phase: n-hexane: isopropyl alcohol: trifluoroacetic acid =80:20:1, wavelength 235 nm, flow rate of 0.5 ml/min.
As can be seen from the above examples, the perovskite LaFeO 3 、LaCoO 3 And LaNiO 3 The yield of the electrode material for preparing the optically active 2-hydroxy-2-phenyl propanoic acid by asymmetrically electro-carboxylating acetophenone is respectively up to 32%, 38% and 40%, and the ee value is respectively up to 86%, 85% and 87%, which is far higher than the asymmetric electro-carboxylation effect of the stainless steel electrode on the 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 within the scope of the claims of the present invention.
Claims (1)
1. The electro-catalysis application of the perovskite electrode material is characterized in that La (NO) is treated by a sol-gel method 3 ) 3 ·6H 2 O is lanthanum source and Fe (NO) 3 ) 3 ·9H 2 O is iron source, co (NO) 3 ) 2 ·6H 2 O is a cobalt source or Ni (NO) 3 ) 2 ·6H 2 Preparing LaBO by using O as nickel source and citric acid monohydrate as complexing agent 3 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 used Ⅱ - (R, R) salen as inducer, n-butanol,Ethanol or isopropanol is taken as a proton source, the electro-carboxylation reaction is carried out under normal pressure saturated carbon dioxide by constant current electrolysis, the 2-hydroxy-2-phenylpropionic acid with optical activity is obtained after rotary evaporation, extraction and purification of reaction liquid, and the electro-catalysis application specifically comprises the following steps:
a. preparation of the electrolyte
Mixing acetophenone with tetra-n-butylammonium iodide and Co Ⅱ Putting electrolyte prepared from (R, R) salen, a proton source and N, N-dimethylformamide according to a molar ratio of 0.5 to 2, 0.01 to 0.1: 0.1 to 1, into a one-chamber type electrolytic cell;
b. electrocarboxylation reaction
Introducing carbon dioxide into an electrolytic cell under normal pressure until the electrolytic cell is saturated, and then introducing carbon dioxide into the electrolytic cell at the concentration of 2 to 7 mA cm -2 Carrying 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
Carrying out reduced pressure rotary evaporation on the liquid at the temperature of 70 to 85 ℃ after electrolysis, removing the solvent of N, N-dimethylformamide, adding hydrochloric acid with the concentration of 1 to 2 mol/L for acidification until the solid in the rotary evaporation liquid is completely dissolved, extracting with 20 mL of analytically pure anhydrous ether for three times each time, combining organic layers in extraction liquid, dehydrating and drying for 1 h by anhydrous magnesium sulfate, filtering, carrying out rotary evaporation on the filtrate at the temperature of 20 to 25 ℃, and removing ether to obtain a product, namely the 2-hydroxy-2-phenylpropionic acid with optical activity;
the LaBO 3 The perovskite electrode material is specifically prepared by the following steps:
a. preparation of the precursor
Adding La (NO) 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O or Ni (NO) 3 ) 2 ·6H 2 O is added according to the molar ratio of metal ions of 1:0.8 to 1.5 is dissolved in 10 to 50 mL of distilled water, the mixture is uniformly mixed, citric acid monohydrate is added in an amount which is 0.8 to 2.0 times of the molar ratio of the total metal ions, then the mixed solution is rotated to evaporate the solvent at the temperature of 70 to 85 ℃, and the obtained wet gel is dried at the temperature of 100 to 180 DEGPreparing fluffy powder as a precursor for 12 to 24 hours;
b. preparation of perovskite electrode material
Grinding the precursor prepared in the above step, and then roasting at 500-1100 ℃ for 4-8 h to obtain a product LaBO 3 A perovskite electrode material, wherein B is Fe, co or Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010353424.1A CN111389406B (en) | 2020-04-29 | 2020-04-29 | Preparation method and electrocatalysis application of perovskite electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010353424.1A CN111389406B (en) | 2020-04-29 | 2020-04-29 | Preparation method and electrocatalysis application of perovskite electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111389406A CN111389406A (en) | 2020-07-10 |
| CN111389406B true CN111389406B (en) | 2023-02-03 |
Family
ID=71418422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010353424.1A Active CN111389406B (en) | 2020-04-29 | 2020-04-29 | Preparation method and electrocatalysis application of perovskite electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111389406B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355682B (en) * | 2021-07-09 | 2023-06-20 | 苏州阳光氢能材料科技有限公司 | Iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569786A (en) * | 2012-01-19 | 2012-07-11 | 大连工业大学 | Perovskite Co-based composite negative electrode material as well as preparation and application thereof |
| CN103789791A (en) * | 2014-02-12 | 2014-05-14 | 华东师范大学 | Electrochemical synthesis method of 2-phenylpropionic acid with optical activity |
| CN109092313A (en) * | 2018-07-27 | 2018-12-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of perovskite catalyst and products thereof and application |
| CN109390598A (en) * | 2018-11-15 | 2019-02-26 | 河北工业大学 | A kind of preparation method and applications of difunctional perofskite type oxide oxygen electrode catalyst |
| CN109453774A (en) * | 2018-10-16 | 2019-03-12 | 华东师范大学 | A kind of preparation method and its electro-catalysis application of nickel series duplex metal nano material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI377090B (en) * | 2008-12-09 | 2012-11-21 | Univ Nat Chiao Tung | Synthesis for a catalysis of novel perovskite compound |
-
2020
- 2020-04-29 CN CN202010353424.1A patent/CN111389406B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569786A (en) * | 2012-01-19 | 2012-07-11 | 大连工业大学 | Perovskite Co-based composite negative electrode material as well as preparation and application thereof |
| CN103789791A (en) * | 2014-02-12 | 2014-05-14 | 华东师范大学 | Electrochemical synthesis method of 2-phenylpropionic acid with optical activity |
| CN109092313A (en) * | 2018-07-27 | 2018-12-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of perovskite catalyst and products thereof and application |
| CN109453774A (en) * | 2018-10-16 | 2019-03-12 | 华东师范大学 | A kind of preparation method and its electro-catalysis application of nickel series duplex metal nano material |
| CN109390598A (en) * | 2018-11-15 | 2019-02-26 | 河北工业大学 | A kind of preparation method and applications of difunctional perofskite type oxide oxygen electrode catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111389406A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Díaz-Sainz et al. | Improving trade-offs in the figures of merit of gas-phase single-pass continuous CO2 electrocatalytic reduction to formate | |
| Wei et al. | Metal–organic framework nanosheet electrocatalysts for efficient H2 production from methanol solution: methanol-assisted water splitting or methanol reforming? | |
| KR101270809B1 (en) | Platinum alloy carbon-supported catalysts | |
| CN109280936B (en) | Preparation method of CuO electrode and application of electrocatalytic synthesis of alcohol compound | |
| CA2466362C (en) | Improved rhodium electrocatalyst and method of preparation | |
| Fu et al. | Electrochemical CO2 reduction to formic acid on crystalline SnO2 nanosphere catalyst with high selectivity and stability | |
| CN108866561A (en) | A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode | |
| CN112647095B (en) | Atomically dispersed bimetallic site anchored nitrogen-doped carbon material and preparation and application thereof | |
| Salonen et al. | Sustainable catalysts for water electrolysis: Selected strategies for reduction and replacement of platinum-group metals | |
| CN109943863A (en) | A kind of method that 2,5- dihydroxymethyl tetrahydrofuran is produced in the reduction of catalytic component based on vanadium electro-catalysis biomass class compound | |
| Pham et al. | Which electrode is better for biomass valorization: Cu (OH) 2 or CuO nanowire? | |
| US20140336037A1 (en) | Electrocatalyst for electrochemical conversion of carbon dioxide | |
| CN111013615A (en) | Preparation method of CoP catalyst with hydrogen precipitation and oxygen precipitation high-efficiency dual functions | |
| Verde et al. | Pt/C obtained from carbon with different treatments and (NH4) 2PtCl6 as a Pt precursor | |
| CN111389406B (en) | Preparation method and electrocatalysis application of perovskite electrode material | |
| Bellini et al. | Energy & chemicals from renewable resources by electrocatalysis | |
| Liu et al. | Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction | |
| Liao et al. | Enabling direct CO2 electrolysis by alkali metal cation substituted membranes in a gas diffusion electrode reactor | |
| Wu et al. | Highly efficient electrocatalytic CO2 reduction over pyrolysis–free conjugated metallophthalocyanine networks in full pH range | |
| Qiang et al. | Liquid flow fuel cell with an electrodeposition-modified nickel foam anode for efficient oxidation of 5-hydroxymethylfurfural to produce 2, 5-furandicarboxylic acid with co-generation of electricity | |
| CN110396699B (en) | Method for pair-wise electrosynthesis of 2, 5-furandicarboxylic acid and 2, 5-dimethyloltetrahydrofuran by vanadium nitride-based catalyst | |
| Shao et al. | Ru Supported on p‐phthalic acid‐Mn Derived from a Mn Metal–Organic Framework for Thermo‐and Electrocatalytic Synthesis of Ethylene‐D4 Glycol | |
| CN113398968A (en) | MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof | |
| CN114214644B (en) | MOFs derived Pd@Cu composite material, preparation method thereof and application thereof in electrocatalytic carbon dioxide | |
| CN115094470B (en) | Hierarchical pore carbon loaded cobalt-ruthenium nano alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |