CN109453774B - Preparation method and electrocatalysis application of nickel-based bimetallic nano material - Google Patents
Preparation method and electrocatalysis application of nickel-based bimetallic nano material Download PDFInfo
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- CN109453774B CN109453774B CN201811203030.7A CN201811203030A CN109453774B CN 109453774 B CN109453774 B CN 109453774B CN 201811203030 A CN201811203030 A CN 201811203030A CN 109453774 B CN109453774 B CN 109453774B
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- acetophenone
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 69
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical group C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 claims description 24
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 10
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000411 inducer Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000003115 supporting electrolyte Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 235000001258 Cinchona calisaya Nutrition 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229960000948 quinine Drugs 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000001358 L(+)-tartaric acid Substances 0.000 claims description 3
- 235000011002 L(+)-tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-LWMBPPNESA-N L-(+)-Tartaric acid Natural products OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- AUONNNVJUCSETH-UHFFFAOYSA-N icosanoyl icosanoate Chemical compound CCCCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCCCC AUONNNVJUCSETH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- LOUPRKONTZGTKE-LHHVKLHASA-N quinidine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@H]2[C@@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-LHHVKLHASA-N 0.000 claims 2
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229960001404 quinidine Drugs 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 238000002390 rotary evaporation Methods 0.000 description 20
- WFOFRQGMZWSZOD-UHFFFAOYSA-N 2-hydroxy-2-phenylpropanoic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1.OC(=O)C(O)(C)C1=CC=CC=C1 WFOFRQGMZWSZOD-UHFFFAOYSA-N 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000005498 polishing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000020477 pH reduction Effects 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910017980 Ag—Sn Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- NWCHELUCVWSRRS-SECBINFHSA-N (2r)-2-hydroxy-2-phenylpropanoic acid Chemical group OC(=O)[C@@](O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-SECBINFHSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001308 synthesis method 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
-
- 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 nickel-based bimetallic nano-material and electrocatalysis application thereof, which is characterized in that common nickel metal salt and other common metal salts are utilized to synthesize the bimetallic nano-material with different molar ratios of nickel-based under normal pressure heating condition by one step, solid electrodes are prepared after washing and vacuum drying, and the solid electrodes are used as a cathode of a one-chamber type electrolytic cell and a magnesium rod anode for acetophenone asymmetric electro-carboxylation and equal asymmetric reactions. Compared with the prior art, the invention has excellent magnetism, high-temperature thermal stability, good electrochemical property and chemical catalytic performance, easy modification of chiral compounds, simple and easy realization of process, cheap and easily obtained raw materials, good stability and catalytic activity in asymmetric reactions such as acetophenone asymmetric electro-carboxylation and the like, and the target product with higher ee value can be obtained, thus being an electro-catalytic material with very good application prospect and ideal.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a preparation method of a nickel-based bimetallic nano material and electrocatalysis application of acetophenone and carbon dioxide asymmetric electro-carboxylation reaction.
Background
In recent years, metal and bimetal nano materialsThe method has the important functions of replacing noble metal catalysts, improving catalytic activity and selectivity and the like in the catalytic field, and is generally concerned (Stamenkovic VR, Mun BS, Arenz M, et al. Nat Mater,2007,6: 241-247.), different bimetallic materials are prepared by regulating and synthesizing around the material composition of the bimetallic materials, the performances of the different bimetallic materials in different catalytic reactions are researched, catalyst materials with higher activity, selectivity and stability are sought, and the research of new catalytic reactions and catalytic reaction mechanisms also become a hotspot problem of research. The Pt-Ni bimetallic nano material prepared by Zhang shows excellent catalytic performance in methanol electrocatalysis reaction (Zhang C, Zhang R, Li X, et al. ACS Appl Mater interfaces.2017,9(35): 29623-32.). Wesley synthesizes Ag-Sn bimetal nano material, and research results show that the Ag-Sn bimetal nano material has higher electrocatalytic activity in carbon dioxide reduction reaction (Luc W, Collins C, Wang S, et al.J. Am Chem Soc.2017,139(5): 1885-93.). However, the reaction conditions of the methods for synthesizing metal and bimetallic nano-materials in most of the researches are complex, and the methods cannot be popularized in industrial application, so that the search for a synthesis method with simple and mild conditions and the preparation of metal and bimetallic nano-materials with low price, easy obtainment and excellent catalytic performance are a great difficulty in research and application. In addition, as one of the important aspects in green chemistry, CO is utilized2There is a great interest in the synthesis of valuable, economically competitive products (l.x.wu, h.wang, j.x.lu, et al.electrochem. commun.,2012,25, 116-118), whereas CO2The synthesis of some optically active compounds combined with asymmetric synthesis is also a difficulty in the research and application of metal and bimetallic nano-materials. Therefore, the nickel-based bimetallic nano-material is synthesized and applied to electrochemical utilization of CO2The asymmetric synthesis reaction (i.e., electro-carboxylation) has great promise in the field of electrocatalysis.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel-based bimetallic nano material and an electrocatalysis application thereof aiming at the defects of the prior art, the metal salt and the nickel metal salt are heated at normal pressure, the bimetallic nano material with different nickel molar ratios is synthesized by a one-step method, and the obtained product is made into a solid electrode which can be used as a cathode and a magnesium rod anode of a one-room type electrolytic cell and used for acetophenone asymmetric electro-carboxylation and equal asymmetric reactions.
The technical scheme for realizing the purpose of the invention is as follows: a method for preparing nickel series bimetal nano material is characterized in that nickel metal salt, other metal salt, deionized water and absolute ethyl alcohol are mixed according to the proportion of 1: 0.2-5: 0.6-2.8: mixing at a molar ratio of 0.3-1.8, dropwise adding a mixed solution of NaOH and hydrazine hydrate during stirring, synthesizing a nickel-based bimetallic nano material at a temperature of 50-75 ℃ by a one-step method, sequentially performing ultrasonic centrifugal washing on a product by deionized water and absolute ethyl alcohol after reaction is finished until a supernatant is clear and transparent, and then performing vacuum drying at a temperature of 50-80 ℃ to prepare the nickel-based bimetallic nano material with the bimetallic molar ratio of 0.2-5.0, wherein the nickel metal salt is nickel nitrate, nickel sulfate, nickel chloride or nickel acetate; the other metal salt is silver nitrate, copper chloride, ferrous sulfate, ferric chloride, cobalt nitrate or cobalt sulfate; the mixed solution of NaOH and hydrazine hydrate is prepared from 50 wt% of NaOH and 50 vol% of hydrazine hydrate according to the volume ratio of 3: 1-3: 5.
The nickel-based bimetallic nano material is microspherical particles with the particle size of 180-220 nm.
The molar ratio of NaOH to hydrazine hydrate is preferably 1: 14.
the nickel metal salt is preferably nickel nitrate.
The molar ratio of the two metal simple substance components of the nickel-based bimetallic nano material is as follows: Ni/M is 0.2-5, preferably Ni/M5/3, wherein M is Ag, Cu, Fe or Co.
The electrocatalysis application of the nickel-based bimetal nano material prepared by the preparation method of the nickel-based bimetal nano material is characterized in that the nickel-based bimetal nano material is used as a solid electrode prepared by a pressurizing sheet-forming method or a coating fixing method, and the solid electrode is used as a cathode of a one-chamber electrolytic cell and an anode of a magnesium rod to carry out acetophenone asymmetric electro-carboxylation reaction according to the following formula (I):
the specific application of the acetophenone asymmetric electro-carboxylation reaction comprises the following steps:
a, step a: pressing the nickel-based bimetallic nano-material into a wafer solid electrode with the diameter of 2cm by adopting a tabletting grinding tool under the pressure of 1-10 MPa, or mixing the nickel-based bimetallic nano-material with sodium carboxymethylcellulose sol according to the weight ratio of 1 g: mixing the components in a weight-volume ratio of 0.1-0.5 mL, uniformly coating the mixture on two sides of carbon paper after ultrasonic dispersion, and airing the mixture at room temperature to prepare a rectangular solid electrode of 2cm multiplied by 2.2 cm.
b, step (b): and (b) taking the solid electrode prepared in the step a as a cathode of a one-chamber electrolytic cell and a magnesium rod anode for electrocatalysis application, and mixing acetophenone, a supporting electrolyte, a chiral inducer, an auxiliary agent and acetonitrile (MeCN) or N, N-Dimethylformamide (DMF) according to the weight ratio of 1: 1-5: 0.01-0.1: 0.01-0.1: 1-2 mol ratio, placing the mixture into a one-chamber type electrolytic cell, and adding CO at normal temperature and normal pressure2In the atmosphere, the concentration of the catalyst is 0.5-4.5 mA/cm2The constant current density of the catalyst is used for carrying out asymmetric electro-carboxylation reaction on acetophenone and carbon dioxide to obtain a target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), and the supporting electrolyte is quaternary ammonium salt, tetra-n-butylammonium iodide (TBAI) or tetraethylammonium iodide (TEAI); the chiral inducer is Cinchonine (CN), Cinchonine (CD), Quinine (QN), Quinine (QD), L- (+) -tartaric acid (L- (+) -TA) or D- (-) -tartaric acid (D- (-) -TA); the auxiliary agent is n-butanol, n-propanol or isopropanol.
The current density is preferably 2.5mA/cm2(ii) a The MeCN or DMF is preferably DMF; the supporting electrolyte is preferably TEAI; the chiral inducer is preferably CD; the adjuvant is preferably n-butanol.
Compared with the prior art, the method has excellent electrochemical property and chemical catalytic performance, is easy to modify chiral compounds, has simple and easily-realized synthesis process and cheap and easily-obtained raw materials, prepares nickel-based bimetallic nano materials with different molar ratios under the same condition, shows good magnetism, thermal stability and catalytic activity in asymmetric reactions such as acetophenone asymmetric electro-carboxylation and the like, and obtains a target product with higher ee value.
Drawings
FIG. 1 is an XRD diagram of bimetallic nanomaterials of Ni, Ag, Ni/Ag 5/3 and Ni/Ag 5/5;
FIG. 2 is a Scanning Electron Microscope (SEM) image of Ni/Ag 5/3 bi-metal nano-material;
FIG. 3 is an XRD pattern of Ni, Cu and Ni/Cu 5/3 bimetal nano materials;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the Ni/Cu 5/3 bimetal nanomaterial;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the Ni/Fe 5/3 bimetal nanomaterial;
FIG. 6 is a Scanning Electron Microscope (SEM) image of Ni/Co5/3 bimetal nanomaterial.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
1.4540g of Ni (NO) were taken3)2·6H2O and 0.5097g AgNO3Dissolving the mixture in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate with the concentration of 50 vol%, reacting at 60 ℃ for 3 hours, respectively ultrasonically centrifuging and washing the product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally performing vacuum drying at 60 ℃ to obtain the product, namely the Ni/Ag 5/3 bimetal nano material.
Referring to the attached figure 1, the above product is characterized by XRD curve, and the Ni/Ag 5/3 bimetal nano material has characteristic peaks of nickel (111), (200) and (220) and characteristic peaks of silver (111), (200), (220) and (311), which shows that the product of example 1 is pure metal nano material of nickel and silver.
Referring to FIG. 2, the above product is characterized by Scanning Electron Microscopy (SEM), and the Ni/Ag 5/3 bimetal nano material is irregular particles with the size of about 200 nm.
Example 2
And (3) adding 0.1g of the prepared Ni/Ag 5/3 bimetal nano material into 0.2mL of sodium carboxymethylcellulose sol, uniformly coating the mixture on two sides of 2cm × 2.2cm carbon paper after ultrasonic dispersion, and naturally airing to obtain the solid electrode prepared from the Ni/Ag 5/3 bimetal nano material.
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of N-butanol are added into a clean one-chamber electrolytic cell, and CO is continuously and slowly introduced2And stirred. Then inserting a solid electrode made of Ni/Ag 5/3 bimetal nano material as a cathode, polishing a processed magnesium rod as an anode, and connecting a constant current meter to form a circuit path, selecting constant direct current of 10mA, wherein the current density is 2.5mA/cm2Until the end of the electro-carboxylation reaction. After removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, then washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 24%, the ee value is 87%, and the target product is mainly S-2-hydroxy-2-phenylpropionic acid.
Example 3
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of L- (+) -tartaric acid (L- (+) -TA) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2And stirred. Then inserting a solid electrode made of Ni/Ag 5/3 bimetal nano material as a cathode, polishing a processed magnesium rod as an anode, and connecting a constant current meter to form a circuit path, selecting constant direct current of 10mA, wherein the current density is 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 17%, the ee value is 72%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 4
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchoni (CN) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2And stirred. Then inserting a solid electrode made of Ni/Ag 5/3 bimetal nano material as a cathode, polishing a processed magnesium rod as an anode, and connecting a constant current meter to form a circuit path, selecting constant direct current of 10mA, wherein the current density is 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 15%, the ee value is 80%, and the main product is R-2-hydroxy-2-phenylpropionic acid.
Example 5
To a clean one-room type electrolytic cell was added 20mL of anhydrous acetonitrile (MeCN), 1mmol of acetophenone, 2mmol of tetra-n-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of n-butanol, and CO was continuously and slowly passed through2Stirring, inserting solid electrode made of Ni/Ag 5/3 bimetal nano material as cathode, polishing treated magnesium rod as anode, and connecting into constant current meter to form circuit path, selecting constant direct current of 10mA, and current density of 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 12%, the ee value is 71%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 6
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone and 2mmol of tetrakisN-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of n-butanol, with continuous slow CO passage2Stirring, inserting solid electrode made of Ni/Ag 5/3 bimetal nano material as cathode, polishing treated magnesium rod as anode, and connecting into constant current meter to form circuit path, selecting constant direct current 14mA, current density 3.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 19%, the ee value is 78%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 7
1.4540g of Ni (NO) were taken3)2·6H2O and 0.8494g of AgNO3Dissolving the mixture in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate with the concentration of 50 vol%, reacting at 60 ℃ for 3 hours, respectively ultrasonically centrifuging and washing a product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally performing vacuum drying at 60 ℃ to obtain the product, namely the Ni/Ag 5/5 bimetal nano material.
Referring to fig. 1, the product is characterized by XRD curve, and the bi-metal nanomaterial of Ni/Ag 5/5 has characteristic peaks of both nickel (111), (200) and (220) and silver (111), (200), (220) and (311), indicating that the product of example 7 is a pure metal nanomaterial of nickel and silver.
Example 8
And adding 0.2mL of sodium carboxymethylcellulose sol into the Ni/Ag 5/5 bimetal nano material prepared in the embodiment 7, performing ultrasonic dispersion, uniformly coating the mixture on two sides of 2cm × 2.2cm carbon paper, and naturally airing to obtain the solid electrode prepared from the Ni/Ag 5/5 bimetal nano material.
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone and 2mmol of tetra-N-butyl iodide were added to a clean one-chamber electrolytic cellAmmonium hydroxide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of n-butanol, and continuously and slowly introducing CO2Stirring, inserting solid electrode made of Ni/Ag 5/5 bimetal nano material as cathode, polishing treated magnesium rod as anode, and connecting into constant current meter to form circuit path, selecting constant direct current of 10mA, and current density of 2.5mA/cm2. And then electrically carboxylating until the reaction is finished. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 20%, the ee value is 67%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 9
0.8724g of Ni (NO) were taken3)2·6H2O and 0.8494g of AgNO3Dissolving the mixture in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate with the concentration of 50 vol%, reacting at 60 ℃ for 3h, respectively ultrasonically centrifuging and washing a product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally performing vacuum drying at 60 ℃ to obtain the product, namely the Ni/Ag 3/5 bimetal nano material.
Example 10
0.1g of the Ni/Ag 3/5 bimetal nano material prepared in the example 9 is added into 0.2mL of sodium carboxymethylcellulose sol, the mixture is uniformly coated on two sides of 2cm x 2.2cm carbon paper after ultrasonic dispersion, and the solid electrode made of the Ni/Ag 3/5 bimetal nano material is obtained after natural airing.
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2Stirring, inserting solid electrode made of Ni/Ag 3/5 bimetal nano material as cathode, polishing treated magnesium rod as anode, connecting into constant current meter to form circuit path, selecting constant direct current of 10mA,the current density is 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 18%, the ee value is 71%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 11
1.4540g of Ni (NO) were taken3)2·6H2O and 0.5114g CuCl2·2H2Dissolving O in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate (50%) with the concentration of 50 vol%, reacting for 3h at the temperature of 60 ℃, respectively ultrasonically centrifuging and washing a product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally performing vacuum drying at the temperature of 60 ℃ to obtain the product, namely the Ni/Cu 5/3 bimetal nano material.
Referring to fig. 3, the product is characterized by XRD curve, and the bi-metal nanomaterial of Ni/Cu 5/3 has characteristic peaks of (111), (200) and (220) of nickel and characteristic peaks of (100), (110) and (111) of copper, indicating that the product of example 11 is a pure metal nanomaterial of nickel and copper.
Referring to FIG. 4, the above product is characterized by Scanning Electron Microscopy (SEM), and the Ni/Cu 5/3 bimetal nano material is a nearly spherical particle with the size of about 200 nm.
Example 12
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2Stirring, inserting solid electrode made of Ni/Cu 5/3 bimetal nano material as cathode, polishing treated magnesium rod as anode, and connecting into constant current meter to form circuit path, selecting constant direct current of 10mA, and current density of 2.5mA/cm2Until the end of the electro-carboxylation reaction. After removing the solvent by rotary evaporation, addingAcidifying with 10mL of 1mol/L HCl, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate, drying for 1h, and performing rotary evaporation to remove ether to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 18%, the ee value is 73%, and the target product is mainly S-2-hydroxy-2-phenylpropionic acid.
Example 13
1.4540g of Ni (NO) were taken3)2·6H2O and 1.2116g of Fe (NO)3)3·9H2Dissolving O in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate with the concentration of 50 vol%, reacting for 3h at the temperature of 60 ℃, respectively ultrasonically centrifuging and washing a product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally carrying out vacuum drying at the temperature of 60 ℃ to obtain the product, namely the Ni/Fe 5/3 bimetal nano material.
Referring to FIG. 5, the above product is characterized by Scanning Electron Microscopy (SEM), and the Ni/F5/3 bimetallic nanomaterial is spherical and has a size of about 200 nm.
Example 14
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2Stirring, inserting solid electrode made of Ni/Fe 5/3 bimetal nano material as cathode, polishing the magnesium rod as anode, connecting into constant current meter to form circuit path, selecting constant direct current of 10mA, and current density of 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 14%, the ee value is 80%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
Example 15
1.4540g of Ni (NO) were taken3)2·6H2O and 0.8731g of Co (NO)3)3·6H2Dissolving O in a mixed solution of 10mL of deionized water and 20mL of absolute ethyl alcohol, continuously stirring, slowly dropwise adding a mixed solution of 30mL of NaOH with the concentration of 1mol/L and 20mL of hydrazine hydrate with the concentration of 50 vol%, reacting for 3h at the temperature of 60 ℃, respectively ultrasonically centrifuging and washing a product with the deionized water and the absolute ethyl alcohol until the supernatant is clear and transparent, and finally carrying out vacuum drying at the temperature of 60 ℃ to obtain the product, namely the Ni/Co5/3 bimetal nano material.
Referring to FIG. 6, the above product is characterized by Scanning Electron Microscopy (SEM), and the Ni/Co5/3 bimetal nanomaterial is nearly spherical and has a size of about 200 nm.
Example 16
20mL of anhydrous N, N-Dimethylformamide (DMF), 1mmol of acetophenone, 2mmol of tetra-N-butylammonium iodide (TBAI), 0.05mmol of Cinchonidine (CD) and 0.05mmol of N-butanol were added to a clean one-chamber electrolytic cell, and CO was continuously and slowly introduced2Stirring, inserting solid electrode made of Ni/Co5/3 bimetal nano material as cathode, polishing treated magnesium rod as anode, and connecting into constant current meter to form circuit path, selecting constant direct current of 10mA, and current density of 2.5mA/cm2Until the end of the electro-carboxylation reaction. Removing the solvent by rotary evaporation, adding 10mL of 1mol/L HCl for acidification, extracting with 30mL of anhydrous ether for 3 times, washing with 10mL of saturated NaCl solution once, adding anhydrous magnesium sulfate for drying for 1h, and then removing the ether by rotary evaporation to obtain the target product 2-hydroxy-2-phenylpropionic acid (2-hydroxy-2-phenylpropionic acid), wherein the yield is 17%, the ee value is 77%, and the main product is S-2-hydroxy-2-phenylpropionic acid).
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 (1)
1. The electrocatalysis application of nickel-based bimetallic nano material is characterized in that nickel metal salt, other metal salt, deionized water and absolute ethyl alcohol are mixed according to the proportion of 1: 0.2-5: 0.6-2.8: 0.3-1.8 mol ratio, dripping a mixed solution of NaOH and hydrazine hydrate in stirring, synthesizing a nickel-based bimetallic nano material by a one-step method at the temperature of 50-75 ℃, sequentially performing ultrasonic centrifugal washing on a product by deionized water and absolute ethyl alcohol after reaction to obtain a clear and transparent supernatant, and then performing vacuum drying at the temperature of 50-80 ℃ to obtain the nickel-based bimetallic nano material with the mol ratio of two metals of 0.2-5.0, wherein a solid electrode prepared by the nickel-based bimetallic nano material by adopting a pressurizing sheet-forming method or a coating and fixing method is used as a cathode of a one-chamber type electrolytic cell and a magnesium rod anode for acetophenone asymmetric electro-carboxylation reaction, and the specific application comprises the following steps:
a, step a: pressing the nickel-based bimetallic nano-material into a wafer solid electrode with the diameter of 2cm by adopting a tabletting grinding tool under the pressure of 1-10 MPa, or mixing the nickel-based bimetallic nano-material with sodium carboxymethylcellulose sol according to the weight ratio of 1 g: mixing the materials in a weight-volume ratio of 0.1-0.5 mL, uniformly coating the mixture on two sides of carbon paper after ultrasonic dispersion, and airing the mixture at room temperature to prepare a rectangular solid electrode of 2cm multiplied by 2.2 cm;
b, step (b): and (b) taking the solid electrode prepared in the step a as a cathode of a one-chamber electrolytic cell and a magnesium rod anode for electrocatalysis application, and mixing the acetophenone, a supporting electrolyte, a chiral inducer, an auxiliary agent and acetonitrile or N, N-dimethylformamide according to the weight ratio of 1: 1-5: 0.01-0.1: 0.01-0.1: 1-2 mol ratio, placing the mixture into a one-chamber type electrolytic cell, and adding CO at normal temperature and normal pressure2In the atmosphere, the concentration of the catalyst is 0.5-4.5 mA/cm2The asymmetric electro-carboxylation reaction of acetophenone and carbon dioxide is carried out at constant current density to obtain a target product 2-hydroxy-2 phenylpropionic acid, and the supporting electrolyte is quaternary ammonium salt, tetra-n-butylammonium iodide or tetraethylammonium iodide; the chiral inducer is cinchonine, cinchonidine, quinine, quinidine, L- (+) -tartaric acid or D- (-) -tartaric acid; the auxiliary agent is n-butanol, n-propanol or isopropanol.
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