CN109453774A - A kind of preparation method and its electro-catalysis application of nickel series duplex metal nano material - Google Patents
A kind of preparation method and its electro-catalysis application of nickel series duplex metal nano material Download PDFInfo
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- CN109453774A CN109453774A CN201811203030.7A CN201811203030A CN109453774A CN 109453774 A CN109453774 A CN 109453774A CN 201811203030 A CN201811203030 A CN 201811203030A CN 109453774 A CN109453774 A CN 109453774A
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- nano material
- nickel
- metal nano
- duplex metal
- series duplex
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 150000002815 nickel Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 title abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 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 23
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 238000005406 washing 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 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 39
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 26
- 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 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 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 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 11
- 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 10
- 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 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 235000001258 Cinchona calisaya Nutrition 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
- 239000002671 adjuvant Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 229960000948 quinine Drugs 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003115 supporting electrolyte Substances 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000010944 silver (metal) Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- KMPWYEUPVWOPIM-LSOMNZGLSA-N cinchonine Chemical compound C1=CC=C2C([C@@H]([C@H]3N4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-LSOMNZGLSA-N 0.000 claims 2
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000000411 inducer Substances 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000021523 carboxylation Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound 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 description 19
- 238000002390 rotary evaporation Methods 0.000 description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 230000020477 pH reduction Effects 0.000 description 10
- 230000037361 pathway Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 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
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 229910017980 Ag—Sn Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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 kind of preparation method of nickel series duplex metal nano material and its electro-catalysis applications, its main feature is that utilizing common nickel metal salt and other common metal salt, the bimetal nano material of one-step synthesis method nickel system different mol ratio under the conditions of normal heating, solid electrode is made after washing vacuum drying, the cathode and magnesium bar anode as a Room type electrolytic cell are for the asymmetric electric carboxylation of acetophenone and wait asymmetric reactions.The present invention has excellent magnetism compared with prior art, high high-temp stability, good electrochemical properties and chemical catalysis performance and the modification for being easy progress chipal compounds, simple process is easily realized, raw material is cheap and easy to get, good stability and catalytic activity are shown in the asymmetric reactions such as the asymmetric electric carboxylation of acetophenone, obtains the target product of higher ee value, is a kind of very promising and very ideal electrocatalysis material.
Description
Technical field
The present invention relates to electrochemical technology field, the preparation method of specifically a kind of nickel series duplex metal nano material and
The electro-catalysis application of its acetophenone and the asymmetric electric carboxylation reaction of carbon dioxide.
Background technique
In recent years, noble metal catalyst, raising catalysis work are substituted in catalytic field due to metal and bimetal nano material
Property and selectivity etc. important function and by common concern (Stamenkovic VR, Mun BS, Arenz M, et
Al.Nat Mater, 2007,6:241-247.), regulation, which is carried out, around bimetallic material composition is synthetically prepared different double gold
Belong to material, studies performance of the above-mentioned different bimetallic material in different catalysis reactions, it is intended to which finding has more high activity, choosing
The catalyst material of selecting property and stability, and the heat for also becoming research with mechanism of catalytic reaction is reacted in the catalysis for attempting to explore newly
Point problem.The Pt-Ni bimetal nano material of Zhang preparation shows superior catalytic performance in methanol electrocatalytic reaction
(Zhang C,Zhang R,Li X,et al.ACS Appl Mater Interfaces.2017,9(35):29623-32.)。
Wesley has synthesized Ag-Sn bimetal nano material, it is with higher in carbon dioxide reduction reaction on result of study surface
Electro catalytic activity (Luc W, Collins C, Wang S, et al.J Am Chem Soc.2017,139 (5): 1885-93.).
But the method reaction condition of synthesis metal and bimetal nano material is more complicated in above-mentioned most of research, can not spread to
In industrial application, thus a kind of simple mild synthetic method of condition is explored, it is excellent to prepare a kind of cheap and easy to get and catalytic performance
Metal and bimetal nano material be its research application a big difficulty.In addition, as in Green Chemistry important one
A aspect, utilizes CO2Synthesize some valuable, with economic competitiveness products attracted very big concern (L.X.Wu,
H.Wang, J.X.Lu, et al.Electrochem.Commun., 2012,25,116-118.), and by CO2With asymmetric syntheses
It is also metal and the difficult point that bimetal nano investigation of materials is applied in conjunction with some compounds with optical activation are synthesized.Cause
This, synthesizes nickel series duplex metal nano material and is applied to electrochemistry using CO2Carry out asymmetric catalysis synthesis (i.e. electric carboxylation
React) there is very big prospect in electro-catalysis field.
Summary of the invention
The purpose of the present invention is the preparations of a kind of nickel series duplex metal nano material of offer in view of the deficiencies of the prior art
Method and its electro-catalysis application utilize normal heating metal salt and nickel metal salt, pair of one-step synthesis method nickel system different mol ratio
Metal nano material is made into solid electrode, can be used as the cathode and magnesium bar anode of a Room type electrolytic cell, not for acetophenone
Symmetrical electricity carboxylation and asymmetric reactions are waited, there is good magnetic, thermal stability and catalytic activity, obtain the target of higher ee value
Product, synthesis technology is simple, and raw material is cheap and easy to get, and the nickel series duplex metal nano material of different proportion can be prepared under the same terms
Material is a kind of very promising modified electrode.
Realizing the technical solution of the object of the invention is: a kind of preparation method of nickel series duplex metal nano material, its main feature is that
Nickel metal salt is mixed with other metal salts, deionized water and dehydrated alcohol by the molar ratio of 1:0.2~5:0.6~2.8:0.3~1.8
It closes, the mixed solution of NaOH and hydrazine hydrate, one-step synthesis method nickel series duplex metal nano at a temperature of 50~75 DEG C is added dropwise in stirring
Material successively carries out ultrasonic centrifuge washing product to supernatant clear with deionized water and dehydrated alcohol after reaction,
Then it is dried in vacuo at a temperature of 50~80 DEG C, the nickel series duplex metal nano material that bimetallic molar ratio is 0.2~5.0 is made,
The nickel metal salt is nickel nitrate, nickel sulfate, nickel chloride or nickel acetate；Other described metal salts are silver nitrate, copper chloride, sulfuric acid
Ferrous iron, iron chloride, cobalt nitrate or cobaltous sulfate；The mixed solution of the NaOH and hydrazine hydrate by 50wt% NaOH and 50vol%
Hydrazine hydrate is configured by 3:1~3:5 volume ratio.
The nickel series duplex metal nano material is the micro-spherical particle of 180~220nm.
The NaOH and preferred 1:14 of hydrazine hydrate molar ratio.
The preferred nickel nitrate of nickel metal salt.
Two metal simple-substance component molar ratios of the nickel series duplex metal nano material are as follows: Ni/M=0.2~5, preferably Ni/M
=5/3, wherein M is Ag, Cu, Fe or Co.
A kind of electro-catalysis application of the nickel series duplex metal nano material of nickel series duplex metal nano material preparation method preparation,
Feature is by nickel series duplex metal nano material using the solid electrode made of method in blocks or coating fixation that pressurizes, as a Room type
The cathode and magnesium bar anode of electrolytic cell, as following formula (I) carries out the asymmetric electric carboxylation reaction of acetophenone:
The concrete application of the asymmetric electric carboxylation reaction of the acetophenone the following steps are included:
A step: using tabletting grinding tool under the pressure of 1~10MPa, nickel series duplex metal nano material, which is pressed into diameter, is
The disk solid electrode of 2cm, or by nickel series duplex metal nano material and sodium carboxymethylcellulose colloidal sol by 1g:0.1~0.5mL weight
Volume ratio mixing is measured, carbon paper two sides is evenly applied to after ultrasonic disperse, dries at room temperature, the rectangular solid of 2cm × 2.2cm is made
Electrode.
B step: cathode and magnesium bar anode using solid electrode prepared by above-mentioned a step as a Room type electrolytic cell carry out electricity
Catalytic applications, by acetophenone and supporting electrolyte, chiral induction agent, adjuvant and acetonitrile (MeCN) or n,N-Dimethylformamide
(DMF) by the molar ratio of 1:1~5:0.01~0.1:0.01~0.1:1~2 mixing after be put into a Room type electrolytic cell, room temperature,
The CO of normal pressure2In atmosphere, with 0.5~4.5mA/cm2Constant current density carry out the electric carboxylation of asymmetry of acetophenone and carbon dioxide
Reaction, obtaining target product is -2 phenylpropionic acid of 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), the support
Electrolyte is quaternary ammonium salt, tetrabutylammonium iodide (TBAI) or tetraethyl ammonium iodide (TEAI)；The chiral induction agent be it is pungent can
Rather (CN), cinchonine fixed (CD), quinine (QN), quinine set (QD), L- (+)-tartaric acid (L- (+)-TA) or D- (-)-tartaric acid
(D-(-)-TA)；The adjuvant is n-butanol, normal propyl alcohol or isopropanol.
The preferred 2.5mA/cm of current density2；The preferred DMF of the MeCN or DMF；The supporting electrolyte is preferred
TEAI；The preferred CD of chiral induction agent；The preferred n-butanol of adjuvant.
The present invention has excellent electrochemical properties and chemical catalysis performance compared with prior art and is easy to carry out chiral
The modification of compound, synthesis technology is simple, Yi Shixian, and raw material is cheap and easy to get, and the nickel of different mol ratio is prepared under the same terms
Series duplex metal nano material shows good magnetic, thermal stability in the asymmetric reactions such as the asymmetric electric carboxylation of acetophenone
And catalytic activity, obtain the target product of higher ee value.
Detailed description of the invention
Fig. 1 is the XRD diagram of 5/5 bimetal nano material of Ni, Ag, Ni/Ag 5/3 and Ni/Ag；
Fig. 2 is scanning electron microscope (SEM) figure of 5/3 bimetal nano material of Ni/Ag；
Fig. 3 is the XRD diagram of 5/3 bimetal nano material of Ni, Cu and Ni/Cu；
Fig. 4 is scanning electron microscope (SEM) figure of 5/3 bimetal nano material of Ni/Cu；
Fig. 5 is scanning electron microscope (SEM) figure of 5/3 bimetal nano material of Ni/Fe；
Fig. 6 is scanning electron microscope (SEM) figure of 5/3 bimetal nano material of Ni/Co.
Specific embodiment
By following specific embodiments, the present invention is described in further detail.
Embodiment 1
Take 1.4540g Ni (NO3)2·6H2O and 0.5097g AgNO3It is dissolved in 10mL deionized water and the anhydrous second of 20mL
In the mixed solution of alcohol and continue to stir, the NaOH and 20mL concentration that 30mL concentration is 1mol/L, which is then slowly added dropwise, is
The mixed solution of 50vol% hydrazine hydrate reacts 3h at a temperature of 60 DEG C, then with deionized water and dehydrated alcohol respectively ultrasound from
Heart washed product is most dried in vacuo through 60 DEG C, obtaining product is 5/3 bimetal nano material of Ni/Ag afterwards to supernatant clear
Material.
Refering to attached drawing 1, above-mentioned product is characterized through XRD curve, and 5/3 bimetal nano material of Ni/Ag has nickel simultaneously
(111), the characteristic peak of (111) of (200) and (220) characteristic peak and silver, (200), (220) and (311), shows embodiment 1
Product be nickel and silver proof gold metal nanometer material.
Refering to attached drawing 2, above-mentioned product is characterized through scanning electron microscope (SEM), and 5/3 bimetal nano material of Ni/Ag is irregular
Particle, size are about 200nm.
Embodiment 2
It takes the 5/3 bimetal nano material of Ni/Ag of the above-mentioned preparation of 0.1g that 0.2mL sodium carboxymethylcellulose colloidal sol is added, surpasses
It is evenly applied to the two sides of the carbon paper of 2cm × 2.2cm after sound dispersion, obtains 5/3 bimetal nano material of Ni/Ag after natural drying
The made solid electrode of material.
The anhydrous n,N-Dimethylformamide of 20mL (DMF) is added into a clean Room type electrolytic cell, 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD), 0.05mmol n-butanol are persistently slowly introducing CO2
And it stirs.Being inserted into the solid electrode made of 5/3 bimetal nano material of Ni/Ag is cathode, the magnesium bar of polished
Make anode, and access galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, until
Electric carboxylation reaction terminates.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, is extracted with the anhydrous ether of 30mL
It taking 3 times, then washed once with 10mL saturation NaCl solution, rotary evaporation removes ether after the dry 1h of anhydrous magnesium sulfate is added,
Obtain target product be -2 phenylpropionic acid of 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield 24%,
Ee value is 87%, predominantly -2 phenylpropionic acid of S-2- hydroxyl (S-2-hydroxy-2-phenylpropionic acid).
Embodiment 3
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol L- (+)-tartaric acid (L- (+)-TA) and 0.05mmol n-butanol, hold
Continuous slowly logical CO2And it stirs.Being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Ag is cathode, is beaten
It grinds processed magnesium bar and makees anode, and access galvanostat and form circuit pathways, select constant dc 10mA, current density is
2.5mA/cm2, until electric carboxylation reaction terminates.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, is used in combination
The anhydrous ether of 30mL extracts 3 times, then washed once with 10mL saturation NaCl solution, and the dry 1h back spin of anhydrous magnesium sulfate is added
Turn evaporation and remove ether, -2 phenylpropionic acid (2-hydroxy-2-phenylpropionic of target product 2- hydroxyl can be obtained
Acid), yield 17%, ee value are 72%, predominantly -2 phenylpropionic acid (S-2-hydroxy-2- of S-2- hydroxyl
phenylpropionic acid)。
Embodiment 4
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol Xin Keni (CN) and 0.05mmol n-butanol continue slowly to lead to CO2And
Stirring.Being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Ag is cathode, the magnesium bar of polished
Make anode, and access galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, until
Electric carboxylation reaction terminates.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, is extracted with the anhydrous ether of 30mL
It taking 3 times, then washed once with 10mL saturation NaCl solution, rotary evaporation removes ether after the dry 1h of anhydrous magnesium sulfate is added,
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid) can be obtained, yield is
15%, ee value are 80%, predominantly -2 phenylpropionic acid of R-2- hydroxyl (S-2-hydroxy-2-phenylpropionic acid).
Embodiment 5
20mL anhydrous acetonitrile (MeCN), 1mmol acetophenone, the positive fourth of 2mmol tetra- are added into a clean Room type electrolytic cell
Base ammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2And stir, then
Being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Ag is cathode, and the magnesium bar of polished makees anode, and
It accesses galvanostat and forms circuit pathways, select constant dc 10mA, current density 2.5mA/cm2, until electric carboxylation is anti-
It should terminate.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with anhydrous ether extraction 3 times of 30mL, so
It washed once afterwards with 10mL saturation NaCl solution, rotary evaporation removes ether after the dry 1h of anhydrous magnesium sulfate is added, and can be obtained
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield 12%, ee value
It is 71%, predominantly -2 phenylpropionic acid of S-2- hydroxyl (S-2-hydroxy-2-phenylpropionic acid).
Embodiment 6
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, it is inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Ag and makees cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 14mA, current density 3.5mA/cm2, directly
Terminate to electric carboxylation reaction.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with the anhydrous ether of 30mL
Then extraction 3 times washed once with 10mL saturation NaCl solution, rotary evaporation removes second after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield can be obtained in ether
It is 78% for 19%, ee value, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Embodiment 7
Take the Ni (NO of 1.4540g3)2·6H2The AgNO of O and 0.8494g3It is anhydrous with 20mL to be dissolved in 10mL deionized water
In the mixed solution of ethyl alcohol and continue to stir, the NaOH and 20mL concentration that 30mL concentration is 1mol/L, which is then slowly added dropwise, is
50vol% hydrazine hydrate mixed solution reacts 3h at a temperature of 60 DEG C, then with the ultrasound centrifugation respectively of deionized water and dehydrated alcohol
Washed product is most dried in vacuo through 60 DEG C, obtaining product is 5/5 bimetal nano material of Ni/Ag afterwards to supernatant clear.
Refering to attached drawing 1, above-mentioned product is characterized through XRD curve, and 5/5 bimetal nano material of Ni/Ag has nickel simultaneously
(111), the characteristic peak of (111) of (200) and (220) characteristic peak and silver, (200), (220) and (311), shows embodiment 7
Product be nickel and silver proof gold metal nanometer material.
Embodiment 8
Take the 5/5 bimetal nano material of Ni/Ag for applying the preparation of embodiment 7 that 0.2mL sodium carboxymethylcellulose colloidal sol is added,
It is evenly applied to the two sides of the carbon paper of 2cm × 2.2cm after ultrasonic disperse, obtains 5/5 bimetal nano of Ni/Ag after natural drying
Solid electrode made by material.
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, being inserted into the solid electrode made by 5/5 bimetal nano material of Ni/Ag is cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2.So
Electric carboxylation is instead until should terminate afterwards.Rotary evaporation removes the 1mol/L HCl acidification that 10mL is added after solvent, anhydrous with 30mL
Ether extracts 3 times, then washed once with 10mL saturation NaCl solution, and rotary evaporation removes after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid) can be obtained in ether, produces
Rate is that 20%, ee value is 67%, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Embodiment 9
Take the Ni (NO of 0.8724g3)2·6H2The AgNO of O and 0.8494g3It is anhydrous with 20mL to be dissolved in 10mL deionized water
In the mixed solution of ethyl alcohol and continue to stir, the NaOH and 20mL concentration that 30mL concentration is 1mol/L, which is then slowly added dropwise, is
The hydrazine hydrate mixed solution of 50vol% reacts 3h at a temperature of 60 DEG C, and with deionized water and dehydrated alcohol, ultrasound centrifugation is washed respectively
Product is washed to supernatant clear, is most dried in vacuo afterwards through 60 DEG C, obtaining product is 3/5 bimetal nano material of Ni/Ag.
Embodiment 10
It is molten that 0.2mL sodium carboxymethylcellulose is added in the 3/5 bimetal nano material of Ni/Ag for taking 0.1g embodiment 9 to prepare
Glue is evenly applied to the two sides of the carbon paper of 2cm × 2.2cm after ultrasonic disperse, obtains 3/5 bimetallic of Ni/Ag after natural drying and receive
Solid electrode made by rice material.
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, being inserted into the solid electrode made by 3/5 bimetal nano material of Ni/Ag is cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, directly
Terminate to electric carboxylation reaction.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with the anhydrous ether of 30mL
Then extraction 3 times washed once with 10mL saturation NaCl solution, rotary evaporation removes second after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield can be obtained in ether
It is 71% for 18%, ee value, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Embodiment 11
Take the Ni (NO of 1.4540g3)2·6H2O and 0.5114g CuCl2·2H2O is dissolved in 10mL deionized water and 20mL
In the mixed solution of dehydrated alcohol and continue to stir, the NaOH and 20mL concentration that 30mL concentration is 1mol/L, which is then slowly added dropwise, is
Hydrazine hydrate (50%) mixed solution of 50vol%, reacts 3h at a temperature of 60 DEG C, ultrasonic respectively with deionized water and dehydrated alcohol
Centrifuge washing product is most dried in vacuo through 60 DEG C, obtaining product is 5/3 bimetal nano material of Ni/Cu afterwards to supernatant clear
Material.
Refering to attached drawing 3, above-mentioned product is characterized through XRD curve, and 5/3 bimetal nano material of Ni/Cu has nickel simultaneously
(111), the characteristic peak of (200) and (100) of (220) characteristic peak and copper, (110) and (111), shows the product of embodiment 11
For the proof gold metal nanometer material of nickel and copper.
Refering to attached drawing 4, above-mentioned product is characterized through scanning electron microscope (SEM), and 5/3 bimetal nano material of Ni/Cu is subsphaeroidal
Particle, size are about 200nm.
Embodiment 12
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Cu is cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, directly
Terminate to electric carboxylation reaction.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with the anhydrous ether of 30mL
Then extraction 3 times washed once with 10mL saturation NaCl solution, rotary evaporation removes second after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield can be obtained in ether
It is 73% for 18%, ee value, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Embodiment 13
Take the Ni (NO of 1.4540g3)2·6H2Fe (the NO of O and 1.2116g3)3·9H2O be dissolved in 10mL deionized water with
In the mixed solution of 20mL dehydrated alcohol and continue to stir, it is dense that NaOH and 20mL that 30mL concentration is 1mol/L is then slowly added dropwise
Degree is the mixed solution of 50vol% hydrazine hydrate, reacts 3h at a temperature of 60 DEG C, with deionized water and dehydrated alcohol respectively ultrasound from
Heart washed product is most dried in vacuo through 60 DEG C, obtaining product is 5/3 bimetal nano material of Ni/Fe afterwards to supernatant clear
Material.
Refering to attached drawing 5, above-mentioned product is characterized through scanning electron microscope (SEM), and Ni/F5/3 bimetal nano material is spherical shape,
Size is about 200nm.
Embodiment 14
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Fe is cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, directly
Terminate to electric carboxylation reaction.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with the anhydrous ether of 30mL
Then extraction 3 times washed once with 10mL saturation NaCl solution, rotary evaporation removes second after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield can be obtained in ether
It is 80% for 14%, ee value, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Embodiment 15
Take the Ni (NO of 1.4540g3)2·6H2Co (the NO of O and 0.8731g3)3·6H2O be dissolved in 10mL deionized water with
In the mixed solution of 20mL dehydrated alcohol and continue to stir, it is dense that NaOH and 20mL that 30mL concentration is 1mol/L is then slowly added dropwise
Degree is the mixed solution of 50vol% hydrazine hydrate, reacts 3h at a temperature of 60 DEG C, with deionized water and dehydrated alcohol respectively ultrasound from
Heart washed product is most dried in vacuo through 60 DEG C, obtaining product is Ni/Co5/3 bimetal nano material afterwards to supernatant clear.
Refering to attached drawing 6, above-mentioned product through scanning electron microscope (SEM) characterize, Ni/Co5/3 bimetal nano material be it is subsphaeroidal,
Its size is about 200nm.
Embodiment 16
Be added into a clean Room type electrolytic cell the anhydrous N,N-dimethylformamide of 20mL (DMF), 1mmol acetophenone,
2mmol tetrabutylammonium iodide (TBAI), 0.05mmol cinchonidine (CD) and 0.05mmol n-butanol continue slowly to lead to CO2
And stir, being inserted into the solid electrode made by 5/3 bimetal nano material of Ni/Co is cathode, the magnesium of polished
Stick makees anode, and accesses galvanostat and form circuit pathways, selects constant dc 10mA, current density 2.5mA/cm2, directly
Terminate to electric carboxylation reaction.Rotary evaporation removes the 1mol/L HCl acidification of addition 10mL after solvent, with the anhydrous ether of 30mL
Then extraction 3 times washed once with 10mL saturation NaCl solution, rotary evaporation removes second after the dry 1h of anhydrous magnesium sulfate is added
- 2 phenylpropionic acid of target product 2- hydroxyl (2-hydroxy-2-phenylpropionic acid), yield can be obtained in ether
It is 77% for 17%, ee value, predominantly -2 phenylpropionic acid (S-2-hydroxy-2-phenylpropionic of S-2- hydroxyl
acid)。
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of the invention patent.
Claims (6)
1. a kind of preparation method of nickel series duplex metal nano material, it is characterised in that by nickel metal salt and other metal salts, go from
Sub- water and dehydrated alcohol are mixed by the molar ratio of 1:0.2 ~ 5:0.6 ~ 2.8:0.3 ~ 1.8, and the mixed of NaOH and hydrazine hydrate is added dropwise in stirring
Close solution, one-step synthesis method nickel series duplex metal nano material at a temperature of 50 ~ 75 DEG C, after reaction successively with deionized water and
Dehydrated alcohol carries out ultrasonic centrifuge washing product to supernatant clear, is then dried in vacuo, is made at a temperature of 50 ~ 80 DEG C
The nickel series duplex metal nano material that two metal molar ratios are 0.2 ~ 5.0, the nickel metal salt are nickel nitrate, nickel sulfate, nickel chloride
Or nickel acetate；Other described metal salts are silver nitrate, copper chloride, ferrous sulfate, iron chloride, cobalt nitrate or cobaltous sulfate；It is described
The mixed solution of NaOH and hydrazine hydrate is configured by the NaOH and 50vol% hydrazine hydrate of 50wt% by 3:1 ~ 3:5 volume ratio.
2. the preparation method of nickel series duplex metal nano material according to claim 1, it is characterised in that the nickel series duplex metal
Nano material is the micro-spherical particle of 180 ~ 220 nm.
3. the preparation method of nickel series duplex metal nano material according to claim 1, it is characterised in that the NaOH and hydration
The preferred 1:14 of hydrazine molar ratio.
4. the preparation method of nickel series duplex metal nano material according to claim 4, it is characterised in that the nickel metal salt is excellent
Select nickel nitrate.
5. according to claim 1 or the preparation method of nickel series duplex metal nano material described in claim 2, it is characterised in that described
Two metal simple-substance component molar ratios of nickel series duplex metal nano material are as follows: Ni/M=0.2 ~ 5, preferably Ni/M=5/3, wherein M be
Ag, Cu, Fe or Co.
6. a kind of electricity of the nickel series duplex metal nano material of the preparation of nickel series duplex metal nano material preparation method described in claim 1
Catalytic applications, it is characterised in that by nickel series duplex metal nano material using the solid electricity made of method in blocks or coating fixation that pressurizes
Cathode and magnesium bar anode of the pole as a Room type electrolytic cell, for the asymmetric electric carboxylation reaction of acetophenone, concrete application includes
Following steps:
A step: using tabletting grinding tool under the pressure of 1 ~ 10 MPa, it is 2 that nickel series duplex metal nano material, which is pressed into diameter,
The disk solid electrode of cm, or by nickel series duplex metal nano material and sodium carboxymethylcellulose colloidal sol by the mL of 1 g:0.1 ~ 0.5 weight
Volume ratio mixing is measured, carbon paper two sides is evenly applied to after ultrasonic disperse, dries at room temperature, the rectangle of the cm of 2 cm × 2.2 is made
Solid electrode；
B step: the cathode using solid electrode prepared by above-mentioned a step as a Room type electrolytic cell carries out electricity with magnesium bar anode and urges
Change application, acetophenone and supporting electrolyte, chiral induction agent, adjuvant and acetonitrile or n,N-Dimethylformamide pressed into 1:1 ~ 5:
It is put into a Room type electrolytic cell after the mixing of the molar ratio of 0.01 ~ 0.1:0.01 ~ 0.1:1 ~ 2, in CO at room temperature and atmospheric ionization2In atmosphere, with
0.5~4.5 mA/cm2Constant current density carry out the electric carboxylation reaction of asymmetry of acetophenone and carbon dioxide, obtaining target product is
- 2 phenylpropionic acid of 2- hydroxyl, the supporting electrolyte are quaternary ammonium salt, tetrabutylammonium iodide or tetraethyl ammonium iodide；The chirality
Inducer is fixed cinchonine, cinchonine, quinine, quinine set, L- (+)-tartaric acid or D- (-)-tartaric acid；The adjuvant is positive
Butanol, normal propyl alcohol or isopropanol.
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| CN110075886A (en) * | 2019-05-31 | 2019-08-02 | 中南林业科技大学 | Ni-based-carbon composite electrocatalyst and preparation method thereof |
| CN111389406A (en) * | 2020-04-29 | 2020-07-10 | 华东师范大学 | Preparation method and electrocatalysis application of perovskite electrode material |
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| CN110075886A (en) * | 2019-05-31 | 2019-08-02 | 中南林业科技大学 | Ni-based-carbon composite electrocatalyst and preparation method thereof |
| CN111389406A (en) * | 2020-04-29 | 2020-07-10 | 华东师范大学 | Preparation method and electrocatalysis application of perovskite electrode material |
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