CN115595624B - Catalyst for electrocatalytic hydrogenation of cinnamaldehyde and preparation method thereof - Google Patents
Catalyst for electrocatalytic hydrogenation of cinnamaldehyde and preparation method thereof Download PDFInfo
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- CN115595624B CN115595624B CN202110769048.9A CN202110769048A CN115595624B CN 115595624 B CN115595624 B CN 115595624B CN 202110769048 A CN202110769048 A CN 202110769048A CN 115595624 B CN115595624 B CN 115595624B
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- cinnamaldehyde
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- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 77
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 76
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002773 nucleotide Substances 0.000 claims abstract description 6
- -1 nucleotide disodium salt Chemical class 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- INTPYBRGLGSMRA-WFIJOQBCSA-L disodium cytidine 5'-monophosphate Chemical compound [Na+].[Na+].O=C1N=C(N)C=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP([O-])([O-])=O)O1 INTPYBRGLGSMRA-WFIJOQBCSA-L 0.000 claims description 3
- AGSQMPPRYZYDFV-ZJWYQBPBSA-L disodium;[(2r,3s,5r)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl phosphate Chemical compound [Na+].[Na+].O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](COP([O-])([O-])=O)[C@@H](O)C1 AGSQMPPRYZYDFV-ZJWYQBPBSA-L 0.000 claims description 3
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 claims description 3
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 claims description 3
- PVBRXXAAPNGWGE-LGVAUZIVSA-L disodium 5'-guanylate Chemical group [Na+].[Na+].C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](COP([O-])([O-])=O)[C@@H](O)[C@H]1O PVBRXXAAPNGWGE-LGVAUZIVSA-L 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims 1
- FYWLYWMEGHCZAX-MCDZGGTQSA-M sodium [(2r,3s,4r,5r)-5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methyl hydrogen phosphate Chemical compound [Na+].C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)([O-])=O)[C@@H](O)[C@H]1O FYWLYWMEGHCZAX-MCDZGGTQSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000872 buffer Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UDMBCSSLTHHNCD-UHFFFAOYSA-N Coenzym Q(11) Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(O)=O)C(O)C1O UDMBCSSLTHHNCD-UHFFFAOYSA-N 0.000 description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 5
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O UDMBCSSLTHHNCD-KQYNXXCUSA-N 0.000 description 5
- 229950006790 adenosine phosphate Drugs 0.000 description 5
- IERHLVCPSMICTF-UHFFFAOYSA-N cytidine monophosphate Natural products O=C1N=C(N)C=CN1C1C(O)C(O)C(COP(O)(O)=O)O1 IERHLVCPSMICTF-UHFFFAOYSA-N 0.000 description 5
- IERHLVCPSMICTF-ZAKLUEHWSA-N cytidine-5'-monophosphate Chemical compound O=C1N=C(N)C=CN1[C@H]1[C@H](O)[C@@H](O)[C@H](COP(O)(O)=O)O1 IERHLVCPSMICTF-ZAKLUEHWSA-N 0.000 description 5
- GYOZYWVXFNDGLU-XLPZGREQSA-N dTMP Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)C1 GYOZYWVXFNDGLU-XLPZGREQSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- RQFCJASXJCIDSX-UHFFFAOYSA-N 14C-Guanosin-5'-monophosphat Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(COP(O)(O)=O)C(O)C1O RQFCJASXJCIDSX-UHFFFAOYSA-N 0.000 description 4
- RQFCJASXJCIDSX-UUOKFMHZSA-N GMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C=NC=2C(=O)NC(N)=NC12)O)O RQFCJASXJCIDSX-UUOKFMHZSA-N 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- 229940083957 1,2-butanediol Drugs 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- SPOMEWBVWWDQBC-UHFFFAOYSA-K tripotassium;dihydrogen phosphate;hydrogen phosphate Chemical compound [K+].[K+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O SPOMEWBVWWDQBC-UHFFFAOYSA-K 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- QGXLVXZRPRRCRP-IDIVVRGQSA-L Adenosine 5'-phosphate disodium Chemical compound [Na+].[Na+].C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])([O-])=O)[C@@H](O)[C@H]1O QGXLVXZRPRRCRP-IDIVVRGQSA-L 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LMPDLIQFRXLCMO-UHFFFAOYSA-L dipotassium;hydrogen phosphate;phosphoric acid Chemical compound [K+].[K+].OP(O)(O)=O.OP([O-])([O-])=O LMPDLIQFRXLCMO-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000003729 nucleotide group Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- 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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for electrocatalytic hydrogenation of cinnamaldehyde and a preparation method thereof, wherein the method comprises the following steps: mixing 138-442 mu L of chloropalladate aqueous solution with the concentration of 10mg/mL with 191-612 mu L of nucleotide disodium salt aqueous solution with the concentration of 10mg/mL according to a proportion, adding 0-671 mu L of water and 500-527 mu L of C2-C5 dihydric alcohol, and uniformly mixing to obtain a mixed solution; immersing foam nickel into the mixed solution, shaking and mixing uniformly, and standing in a metal bath at 70-100 ℃ for 0.4-2h in a dark place. The method is simple, short in period, easy to control and stable in conditions, green and pollution-free; in the H-type electrolytic tank, an external direct current power supply can realize electrochemical hydrogenation of cinnamaldehyde, and the reaction condition is mild and the catalytic activity is high.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a preparation method of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde.
Background
The selective hydrogenation of carbonyl bonds of unsaturated aldehydes to form the corresponding unsaturated alcohols has been of great interest because of the wide variety of applications of these products in industry. Cinnamaldehyde is a typical unsaturated aldehyde, and the hydrogenation products of cinnamaldehyde include cinnamyl alcohol, 3-phenylpropionaldehyde, and 3-phenylpropanol due to the competitive hydrogenation of c=c and c=o bonds. Cinnamyl alcohol is an important organic aromatic compound and is widely used as an organic synthesis intermediate in perfumes, medicines and other chemical production processes. In industry, ethanol or methanol is mainly used as a solvent, potassium borohydride is used for reducing cinnamyl aldehyde in an alkaline medium (pH=12-14), and the cinnamyl alcohol finished product is obtained through reduced pressure distillation. Although the application in industrial production is wide, the defects of high energy consumption, complex operation and the like exist, the selective hydrogenation of C=O by a hot hydrogenation mode and a catalyst are mainly researched at present, and the reaction condition of high temperature and high pressure [ APPLIED CATALYSIS B: environmental 218 (2017) 591-599] can not be got rid of. At present, few reports about electrocatalytic cinnamaldehyde selective hydrogenation are provided, so that the development of a simple and efficient catalyst with the electrocatalytic cinnamaldehyde selective hydrogenation activity has important practical significance [ ACS catalyst.2019, 9,11307-11316].
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a catalyst for electrocatalytic hydrogenation of cinnamaldehyde.
The second purpose of the invention is to provide a preparation method of the catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which has the advantages of simple process, short period, mild condition, easy control and high efficiency.
The third object of the invention is to provide an application of the catalyst for electrocatalytic hydrogenation of cinnamaldehyde in electrocatalytic hydrogenation reaction of cinnamaldehyde.
The technical scheme of the invention is summarized as follows:
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: mixing 138-442 mu L of chloropalladate aqueous solution with the concentration of 10mg/mL with 191-612 mu L of nucleotide disodium salt aqueous solution with the concentration of 10mg/mL according to a proportion, adding 0-671 mu L of water and 500-527 mu L of C2-C5 dihydric alcohol, and uniformly mixing to obtain a mixed solution; immersing foam nickel into the mixed solution, shaking and mixing uniformly, and standing in a metal bath at 70-100 ℃ for 0.4-2h in a dark place.
The chloropalladate is sodium chloropalladate or potassium chloropalladate.
The nucleotide disodium salt is guanosine 5 '-monophosphate (GMP) disodium salt, cytidine 5' -monophosphate (CMP) disodium salt, thymidine 5 '-monophosphate (TMP) disodium salt or adenosine 5' -monophosphate (AMP) disodium salt.
The C2-C5 glycol is preferably ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol or 1, 5-pentanediol.
The temperature is preferably 80 ℃.
The time for keeping the metal bath away from light is preferably 0.5h.
The catalyst for electrocatalytic hydrogenation of cinnamaldehyde prepared by the preparation method is provided.
The catalyst is applied to the electrocatalytic hydrogenation reaction of cinnamaldehyde.
The method is simple, short in period, easy to control and stable in conditions, green and pollution-free; in the H-type electrolytic tank, an external direct current power supply can realize electrochemical hydrogenation of cinnamaldehyde, and the reaction condition is mild and the catalytic activity is high.
Drawings
FIG. 1 is a scanning electron microscope image of the catalyst prepared in example 3, wherein a is a scanning electron microscope image at 20 μm; b is a scanning electron micrograph at 2 μm;
FIG. 2 is a graph showing hydrogenation results of the catalyst prepared in example 3 at different current densities;
FIG. 3 is a graph showing the hydrogenation results of the catalyst prepared in example 3 at various temperatures;
FIG. 4 is a graph showing the hydrogenation results of the catalyst prepared in example 3 at different substrate concentrations;
FIG. 5 is a graph showing the hydrogenation results of the catalyst prepared in example 3 at various times;
FIG. 6 is a graph showing the hydrogenation results of catalysts prepared from different disodium salts of nucleotides.
Detailed Description
The following examples are intended to enable those skilled in the art to better understand the present invention and are not intended to limit the present invention in any way.
Guanosine 5' -monophosphate is abbreviated as GMP; cytidine-5' -monophosphate is abbreviated as CMP; thymidine-5' -monophosphate is abbreviated as TMP; adenosine 5' -monophosphate is referred to as AMP.
Example 1
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 138 mu L of potassium chloropalladate aqueous solution with the concentration of 10mg/mL and 191 mu L of TMP disodium salt aqueous solution with the concentration of 10mg/mL are mixed, 671 mu L of water and 500 mu L of 1, 2-butanediol are added, and the mixture is uniformly mixed to obtain a mixed solution; immersing foam nickel into the mixed solution, shaking and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place.
Experiments prove that 1, 3-butanediol and 1, 4-butanediol are used for replacing the 1, 2-butanediol of the embodiment, and other products with similar properties to the catalyst for electrocatalytic hydrogenation of cinnamaldehyde prepared in the embodiment are obtained.
Example 2
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 442 mu L of sodium chloropalladate water solution with the concentration of 10mg/mL and 612 mu L of CMP disodium salt water solution with the concentration of 10mg/mL are mixed, 527 mu L of 1, 2-propylene glycol is added, and the mixture is obtained; immersing foam nickel into the mixed solution, shaking and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place.
Experiments prove that 1, 3-propanediol is used for replacing the 1, 2-propanediol of the embodiment, and other materials are the same as the embodiment, so that the product with similar properties to the catalyst for electrocatalytic hydrogenation of cinnamaldehyde prepared by the embodiment is obtained.
Example 3
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 276 mu L of sodium chloropalladate water solution with the concentration of 10mg/mL and 383 mu L of GMP disodium salt water solution with the concentration of 10mg/mL are mixed, 341 mu L of water and 500 mu L of ethylene glycol are added, and the mixture is obtained; immersing foam nickel into the mixed solution, vibrating and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place to obtain the catalyst for electrocatalytic hydrogenation of cinnamaldehyde (GMP-Pd/NF catalyst for short).
See fig. 1a and b.
Example 4
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: mixing 210 mu L of potassium chloropalladate water solution with the concentration of 10mg/mL with 291 mu L of AMP disodium salt water solution with the concentration of 10mg/mL, adding 500 mu L of water and 500 mu L of 1, 2-pentanediol, and uniformly mixing to obtain a mixed solution; immersing foam nickel into the mixed solution, shaking and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place.
Experiments prove that 1, 2-pentanediol in the embodiment is replaced by 1, 3-pentanediol, 1, 4-pentanediol or 1, 5-pentanediol, and other products with similar properties to the catalyst for electrocatalytic hydrogenation of cinnamaldehyde prepared in the embodiment are obtained.
Experiments prove that the corresponding catalyst for electrocatalytic hydrogenation of cinnamaldehyde is prepared by replacing 80 ℃ in the embodiment with any value between 70 ℃ and 100 ℃, such as 70 ℃, 85 ℃, 90 ℃ and 100 ℃.
Experiments prove that the catalyst for electrocatalytic hydrogenation of cinnamaldehyde is prepared by replacing 0.5h in the embodiment with any value of 0.4-2h, such as 2h, 1.5h, 1.4h, 1.3h, 1.0h, 0.8h, 0.6h and 0.4 h.
Example 5
The application of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde in an electrocatalytic hydrogenation reaction of cinnamaldehyde comprises the following steps:
An H-type electrolytic tank is adopted for electrolytic reaction, a direct current power supply is used for providing constant current, the middle of the H-type electrolytic tank is separated by a proton exchange membrane Nafion 117 to form a cathode chamber and an anode chamber, a platinum sheet is an anode chamber electrode, 20mL of 0.05M sulfuric acid aqueous solution is taken as an anolyte, a catalyst for electrocatalytic hydrogenation of cinnamaldehyde (called GMP-Pd/NF catalyst for short) prepared in the embodiment 3 is taken as a cathode chamber electrode, 20mL of catholyte is added, the final concentration of cinnamaldehyde in the catholyte is 0.05M, the final concentration of buffer (dipotassium hydrogen phosphate-potassium dihydrogen phosphate buffer with pH of 7.0, PBS 7) is 0.1M, the balance is acetonitrile aqueous solution with volume concentration of 50%, the current density is sequentially set to be 5mA/cm 2、10mA/cm2、20mA/cm2、30mA/cm2 at 15 ℃, and the constant current is electrolyzed for 6H.
Extracting the reacted catholyte with ethyl acetate, wherein the volume ratio of the ethyl acetate to the catholyte is 1:2, standing for complete layering, and analyzing by gas chromatography, so that the method can sequentially obtain:
Cinnamaldehyde 38.2% conversion, cinnamyl alcohol 83.4% selectivity.
Cinnamaldehyde 71.1% conversion, cinnamyl alcohol 90.3% selectivity.
Cinnamaldehyde 96.3% conversion, cinnamyl alcohol 88.6% selectivity.
Cinnamaldehyde 98.6% conversion, cinnamyl alcohol 85.3% selectivity. See fig. 2.
Example 6
The application of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde in an electrocatalytic hydrogenation reaction of cinnamaldehyde comprises the following steps:
An H-type electrolytic tank is adopted for electrolytic reaction, a direct current power supply is used for providing constant current, the middle of the H-type electrolytic tank is separated by a proton exchange membrane Nafion 117 to form a cathode chamber and an anode chamber, a platinum sheet is an anode chamber electrode, 20mL of 0.05M sulfuric acid aqueous solution is an anolyte, a catalyst for electrocatalytic hydrogenation of cinnamaldehyde (called GMP-Pd/NF catalyst for short) prepared in the embodiment 3 is an anode chamber electrode, 20mL of catholyte is added, the final concentration of cinnamaldehyde in the catholyte is 0.05M, the final concentration of buffer (potassium dihydrogen phosphate-potassium dihydrogen phosphate buffer with the pH of 7.0, PBS 7) is 0.1M, the balance is acetonitrile aqueous solution with the volume concentration of 50 percent, and the constant current density is 10mA/cm 2 for electrolytic 6H under the conditions of 15 ℃,30 ℃ and 50 ℃ respectively.
Extracting the reacted catholyte with ethyl acetate, wherein the volume ratio of the ethyl acetate to the catholyte is 1:2, standing for complete layering, and analyzing by gas chromatography, so that the method can sequentially obtain:
cinnamaldehyde 71.1% conversion, cinnamyl alcohol 90.3% selectivity.
Cinnamaldehyde 81.5% conversion and cinnamyl alcohol 87.7% selectivity.
Cinnamaldehyde 60.5% conversion, cinnamyl alcohol 75.6% selectivity. See fig. 3.
Example 7
The application of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde in an electrocatalytic hydrogenation reaction of cinnamaldehyde comprises the following steps:
An H-type electrolytic tank is adopted for electrolytic reaction, a direct current power supply is used for providing constant current, the middle of the H-type electrolytic tank is separated by a proton exchange membrane Nafion 117 to form a cathode chamber and an anode chamber, a platinum sheet is an anode chamber electrode, 20mL of 0.05M sulfuric acid aqueous solution is an anolyte, a catalyst for electrocatalytic hydrogenation of cinnamaldehyde (called GMP-Pd/NF catalyst for short) prepared in the embodiment 3 is an anode chamber electrode, 20mL of catholyte is added, the final concentration of cinnamaldehyde in the catholyte is respectively 0.025, 0.05 and 0.075M, the final concentration of buffer (pH 7.0 dipotassium hydrogen phosphate-potassium dihydrogen phosphate buffer, PBS 7) is 0.1M, the balance is acetonitrile aqueous solution with the volume concentration of 50 percent, and the constant current density is 10mA/cm 2 for electrolysis for 6H under the condition of 15 ℃.
Extracting the reacted catholyte with ethyl acetate, wherein the volume ratio of the ethyl acetate to the catholyte is 1:2, standing for complete layering, and analyzing by gas chromatography, so that the method can sequentially obtain:
Cinnamaldehyde 97.8% conversion, cinnamyl alcohol 86.1% selectivity.
Cinnamaldehyde 71.1% conversion, cinnamyl alcohol 90.3% selectivity.
Cinnamaldehyde 57.3% conversion, cinnamyl alcohol 88.5% selectivity. See fig. 4.
Example 8
The application of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde in an electrocatalytic hydrogenation reaction of cinnamaldehyde comprises the following steps:
An H-type electrolytic tank is adopted for electrolytic reaction, a direct current power supply is used for providing constant current, the middle of the H-type electrolytic tank is separated by a proton exchange membrane Nafion 117 to form a cathode chamber and an anode chamber, a platinum sheet is an anode chamber electrode, 20mL of 0.05M sulfuric acid aqueous solution is an anolyte, a catalyst for electrocatalytic hydrogenation of cinnamaldehyde (called GMP-Pd/NF catalyst for short) prepared in the embodiment 3 is an anode chamber electrode, 20mL of catholyte is added, the final concentration of cinnamaldehyde in the catholyte is 0.05M, the final concentration of buffer (potassium dihydrogen phosphate-potassium dihydrogen phosphate buffer with pH of 7.0, PBS 7) is 0.1M, the balance is acetonitrile aqueous solution with volume concentration of 50%, and constant current density of 10mA/cm 2 is respectively electrolyzed for 4, 6, 8 and 10H at 15 ℃.
Extracting the reacted catholyte with ethyl acetate, wherein the volume ratio of the ethyl acetate to the catholyte is 1:2, standing for complete layering, and analyzing by gas chromatography, so that the method can sequentially obtain:
Cinnamaldehyde 65.2% conversion, cinnamyl alcohol 87.1% selectivity.
Cinnamaldehyde 71.1% conversion, cinnamyl alcohol 90.3% selectivity.
Cinnamaldehyde conversion rate of 72.7% and cinnamyl alcohol selectivity of 87.8%.
Cinnamaldehyde 78.8% conversion, cinnamyl alcohol 90.6% selectivity, see figure 5.
Example 9
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 276 mu L of sodium chloropalladate water solution with the concentration of 10mg/mL and 345 mu L of CMP disodium salt water solution with the concentration of 10mg/mL are mixed, 379 mu L of water and 500 mu L of glycol are added, and the mixture is obtained; immersing foam nickel into the mixed solution, vibrating and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place to obtain the catalyst for electrocatalytic hydrogenation of cinnamaldehyde (CMP-Pd/NF catalyst for short, wherein the molar ratio of palladium to CMP is 1:1).
Example 10
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 276 mu L of sodium chloropalladate water solution with the concentration of 10mg/mL and 344 mu L of TMP disodium salt water solution with the concentration of 10mg/mL are mixed, 380 mu L of water and 500 mu L of glycol are added, and the mixture is obtained; immersing foam nickel into the mixed solution, vibrating and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place to obtain the catalyst for electrocatalytic hydrogenation of cinnamaldehyde (TMP-Pd/NF catalyst for short, wherein the molar ratio of palladium to TMP is 1:1).
Example 11
A method for preparing a catalyst for electrocatalytic hydrogenation of cinnamaldehyde, which comprises the following steps: 276 mu L of sodium chloropalladate water solution with the concentration of 10mg/mL and 326 mu L of AMP disodium salt water solution with the concentration of 10mg/mL are mixed, 398 mu L of water and 500 mu L of ethylene glycol are added, and the mixture is obtained; immersing foam nickel into the mixed solution, vibrating and mixing uniformly, and standing in a metal bath at 80 ℃ for 0.5h in a dark place to obtain the catalyst for electrocatalytic hydrogenation of cinnamaldehyde (AMP-Pd/NF catalyst for short, wherein the molar ratio of palladium to AMP is 1:1).
Example 12
The application of a catalyst for electrocatalytic hydrogenation of cinnamaldehyde in an electrocatalytic hydrogenation reaction of cinnamaldehyde comprises the following steps: an H-type electrolytic tank is adopted for electrolytic reaction, a direct current power supply is used for providing constant current, the middle of the H-type electrolytic tank is separated by a proton exchange membrane Nafion 117 to form a cathode chamber and an anode chamber, a platinum sheet is an anode chamber electrode, 20mL of 0.05M sulfuric acid aqueous solution is used as an anolyte, a GMP-Pd/NF catalyst (prepared in example 3), a CMP-Pd/NF catalyst (prepared in example 9), a TMP-Pd/NF catalyst (prepared in example 10) and an AMP-Pd/NF catalyst (prepared in example 11) are respectively used as cathode chamber electrodes, 20mL of catholyte is added, the final concentration of cinnamaldehyde in the catholyte is 0.05M, the final concentration of buffer (dipotassium hydrogen phosphate-monopotassium phosphate buffer with pH of 7.0, PBS 7) is 0.1M, the balance is acetonitrile aqueous solution with the volume concentration of 50%, and the constant current density is 10mA/cm 2 at 15 ℃ for 6H.
Extracting the reacted catholyte with ethyl acetate, wherein the volume ratio of the ethyl acetate to the catholyte is 1:2, standing for complete layering, and analyzing by gas chromatography, so that the method can sequentially obtain:
cinnamaldehyde 71.1% conversion, cinnamyl alcohol 90.3% selectivity.
Cinnamaldehyde 71.4% conversion, cinnamyl alcohol 81.5% selectivity.
Cinnamaldehyde 52.6% conversion, cinnamyl alcohol 68.7% selectivity.
Cinnamaldehyde 71.3% conversion, cinnamyl alcohol 84.8% selectivity. See fig. 6.
Experiments prove that the catalyst prepared in the example 1 is used for replacing the catalyst prepared in the example 10 in the example, and the conversion rate of cinnamaldehyde is similar to that of the catalyst prepared in the example 10 except that the catalyst is similar to that of the example; its cinnamyl alcohol selectivity was similar to the catalyst prepared in example 10.
The catalyst prepared in example 2 was used in place of the catalyst prepared in example 9 in this example, except that the conversion of cinnamaldehyde was similar to that of the catalyst prepared in example 9; its cinnamyl alcohol selectivity was similar to the catalyst prepared in example 9.
The catalyst prepared in example 4 was used in place of the catalyst prepared in example 11 in this example, except that the conversion of cinnamaldehyde was similar to that of the catalyst prepared in example 11; its cinnamyl alcohol selectivity was similar to the catalyst prepared in example 11.
Claims (7)
1. The preparation method of the catalyst for electrocatalytic hydrogenation of cinnamaldehyde is characterized by comprising the following steps of: mixing 138-442 mu L of chloropalladate aqueous solution with the concentration of 10mg/mL with 191-612 mu L of nucleotide disodium salt aqueous solution with the concentration of 10mg/mL according to a proportion, adding 0-671 mu L of water and 500-527 mu L of C2-C5 dihydric alcohol, and uniformly mixing to obtain a mixed solution; immersing foam nickel into the mixed solution, vibrating and mixing uniformly, and standing in a metal bath at 70-100 ℃ for 0.4-2h in a dark place;
the nucleotide disodium salt is guanosine-5 '-monophosphate disodium salt, cytidine-5' -monophosphate disodium salt, thymidine-5 '-monophosphate disodium salt or adenosine-5' -monophosphate disodium salt.
2. The preparation method according to claim 1, wherein the chloropalladate is sodium chloropalladate or potassium chloropalladate.
3. The process according to claim 1, wherein the C2-C5 glycol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 2-pentylene glycol, 1, 3-pentylene glycol, 1, 4-pentylene glycol or 1, 5-pentylene glycol.
4. The method according to claim 1, wherein the temperature is 80 ℃.
5. The preparation method according to claim 1, wherein the metal bath is kept stand for 0.5h in a dark place.
6. A catalyst for electrocatalytic hydrogenation of cinnamaldehyde prepared by the preparation method of any one of claims 1 to 5.
7. Use of the catalyst of claim 6 in electrocatalytic hydrogenation of cinnamaldehyde.
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| PL3212601T3 (en) * | 2014-10-30 | 2020-07-13 | Organofuel Sweden Ab | A mild catalytic reduction of c-o bonds and c=o bonds using a recyclable catalyst system |
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