CN115595625A - Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis - Google Patents
Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis Download PDFInfo
- Publication number
- CN115595625A CN115595625A CN202110769051.0A CN202110769051A CN115595625A CN 115595625 A CN115595625 A CN 115595625A CN 202110769051 A CN202110769051 A CN 202110769051A CN 115595625 A CN115595625 A CN 115595625A
- Authority
- CN
- China
- Prior art keywords
- palladium catalyst
- cinnamyl alcohol
- chloropalladate
- electrolytic cell
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 title claims abstract description 56
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 52
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims abstract description 11
- 229940117916 cinnamic aldehyde Drugs 0.000 claims abstract description 11
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 12
- 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 6
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- 235000011009 potassium phosphates Nutrition 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 20
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XARVANDLQOZMMJ-CHHVJCJISA-N 2-[(z)-[1-(2-amino-1,3-thiazol-4-yl)-2-oxo-2-(2-oxoethylamino)ethylidene]amino]oxy-2-methylpropanoic acid Chemical class OC(=O)C(C)(C)O\N=C(/C(=O)NCC=O)C1=CSC(N)=N1 XARVANDLQOZMMJ-CHHVJCJISA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a palladium catalyst, a preparation method and application thereof in cinnamyl alcohol electrosynthesis, wherein the preparation method comprises the following steps: 1) Adding chloropalladate into the tin oxide water dispersion liquid, and stirring; 2) Adding dimethylamine borane aqueous solution into the mixed solution obtained in the step 1), reacting, separating out precipitate, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst. The method is a one-pot synthesis method, and is simple and repeatable. The palladium catalyst is dispersed in the catholyte in a slurry state, so that the contact area of the palladium catalyst and a reactant is increased, and a higher active surface area is generated; the palladium catalyst is easier to separate and regenerate when poisoned; the palladium catalyst has higher catalytic effect on the selective electro-hydrogenation of the cinnamaldehyde to the cinnamyl alcohol, and does not generate polymer byproducts.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a palladium catalyst, a preparation method and application thereof in cinnamyl alcohol electrosynthesis.
Background
Electrocatalytic hydrogenation is a sustainable process approach for the mild upgrading of chemicals and fuels. Compared with the traditional thermocatalytic hydrogenation, the synthesis by utilizing the organic electrochemical hydrogenation reaction has the advantages that: electron replacing H 2 The reaction temperature and the reaction pressure are milder; the process flow is simple, and the requirement on reaction equipment is low; the hydrogenation substrate is widely positioned; the product selectivity and conversion rate can be controlled more easily by adjusting the electrode potential or current density, and the generation of waste and by-products can be reduced. Therefore, at present, sustainable development is vigorously advocated, and electrocatalytic hydrogenation is a necessary way for the continuous and vigorous development of organic synthesis.
Cinnamic aldehyde is one of alpha, beta-unsaturated aldehyde, and the main product cinnamic alcohol of selective hydrogenation has great added value because of being widely applied to the production of medical intermediates, chemicals, perfume and essence. How to only hydrogenate carbon-oxygen double bonds of cinnamaldehyde to obtain a target product cinnamyl alcohol becomes a great research hotspot of selective hydrogenation of unsaturated aldehyde at present. Thermodynamically, the hydrogenation reaction of the carbon-carbon double bond occurs more easily than the hydrogenation reaction of the carbon-oxygen double bond, which also makes the high yield of cinnamyl alcohol not easily available. Therefore, it is very important to prepare a catalyst having both high activity and high selectivity for hydrogenation of carbon-oxygen double bonds. At present, in the field of thermal catalysis, noble metal Pt series and Pt alloy catalysts are most used in the field of selective hydrogenation of unsaturated aldehyde, and the noble metal Pt is proved to have better selectivity on carbon-oxygen double bonds. However, pt has a poor performance in electrochemical hydrogenation because it has an excellent hydrogen evolution effect when used electrochemically as a cathode electrode. RuO of Chongqing university Wei Zidong teacher with good electrochemical selective hydrogenation effect on unsaturated aldehyde 2 -SnO 2 -TiO 2 Ti Electrode (ACS Catal.2019,9, 11307-11316) as RuO 2 SnO as an active center for cinnamic aldehyde adsorption and cinnamic alcohol production 2 The doping can effectively reduce the utilization rate of Ru and improve the current efficiency. When the catalyst is used as a cathode electrode, inAt a conversion of 58.00%, the selectivity of cinnamyl alcohol was 88.86%. However, the catholyte used in the electrolysis reaction is an acidic solution, has a certain corrosivity to equipment and the like, and generates byproducts in the reaction process.
In the prior art, noble metal catalysts are always active in organic electrochemical hydrogenation reactions, but are not much specialized in the selective hydrogenation of unsaturated aldehydes. Palladium catalysts are not noticed in the selective hydrogenation of electrochemically unsaturated aldehydes because of their apparent selectivity for carbon-carbon double bonds in thermocatalysis. Therefore, it is important to research how to improve the selectivity of the palladium catalyst in unsaturated aldehyde for carbon-oxygen double bond hydrogenation by regulating the electrolysis condition and regulating the growth of the palladium catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a palladium catalyst.
The second object of the present invention is to provide a method for preparing a palladium catalyst.
The third purpose of the invention is to provide the application of the palladium catalyst in the electro-synthesis of cinnamyl alcohol.
The technical scheme of the invention is summarized as follows:
a preparation method of a palladium catalyst comprises the following steps:
1) Adding chloropalladate into 100-200mg/L tin oxide water dispersion liquid, and stirring for 8-12 h; the mass ratio of the chloropalladate to the tin oxide is 1 (3-6);
2) Adding 8.5-17mL of dimethylamine borane aqueous solution with the concentration of 0.4-0.8 mg/mL into 200mL of the mixed solution obtained in the step 1) according to the volume ratio, reacting for 12-30 h, separating out precipitates, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst.
The stirring time in step 1) is preferably 9h.
The chloropalladate is preferably sodium or potassium chloropalladate.
A palladium catalyst prepared by the above method.
The application of the palladium catalyst in the electro-synthesis of cinnamyl alcohol is provided.
Preferably, the method comprises the following steps:
1) Dispersing 30-70 mg of palladium catalyst and 0.8-2 mmoL of cinnamaldehyde in 20mL of cathode electrolyte according to the proportion;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anode electrolytic cell;
3) And inserting the working electrode into the liquid in the cathode electrolytic cell, inserting the auxiliary electrode into the anolyte, electrifying, and reacting to obtain the cinnamyl alcohol.
The preferred volume ratio of catholyte is 1: (1-1.5) a mixture of a neutral potassium phosphate aqueous solution having a concentration of 0.05-0.1 mol/L and acetonitrile.
The anolyte is H with 0.025-0.075 mol/L 2 SO 4 An aqueous solution.
The working electrode is preferably a Ti mesh electrode; the auxiliary electrode is a Pt sheet electrode.
The current electrified in the step (3) is 40-60 mA, and the electrifying time is 2-3 hours.
Has the beneficial effects that:
(1) The preparation method of the palladium catalyst is one-pot synthesis, and the preparation method is simple and has repeatability.
(2) The palladium catalyst is dispersed in the catholyte in a slurry state, so that the contact area of the palladium catalyst and a reactant is increased, and a higher active surface area is generated; the palladium catalyst is easier to separate and regenerate when poisoned; the working electrode adopts a purchasing mode, and is simpler and more effective.
(3) The palladium catalyst has higher catalytic effect on the selective electro-hydrogenation of the cinnamaldehyde to the cinnamyl alcohol, and does not generate polymer series byproducts.
The active components of the palladium catalyst are mainly distributed on the surface of the carrier, so that more active sites can be exposed, sufficient active hydrogen is generated, and the utilization rate of palladium atoms is improved. The palladium catalyst of the invention improves the application potential of noble metal palladium in the aspect of carbon-oxygen double bond electrochemical hydrogenation.
Drawings
FIG. 1 is a transmission electron micrograph of a palladium catalyst prepared in example 1.
FIG. 2 is a transmission electron micrograph of the palladium catalyst prepared in example 2.
Fig. 3 is a transmission electron micrograph of the palladium catalyst prepared in example 3.
FIG. 4 is a graph comparing catalytic activities of the palladium catalysts prepared in examples 1 to 3 and comparative example 1.
Detailed Description
The following examples are intended to enable a person skilled in the art to better understand the present invention without, however, limiting it in any way.
Example 1
A preparation method of a palladium catalyst comprises the following steps:
1) Adding potassium chloropalladate into the tin oxide water dispersion liquid with the concentration of 200mg/L, and stirring for 12 hours; the mass ratio of the potassium chloropalladate to the tin oxide is 1:6;
2) Adding 17mL of dimethylamine borane aqueous solution with the concentration of 0.4mg/mL into 200mL of the mixed solution obtained in the step 1), reacting for 12 hours, separating out precipitate, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst. The average particle diameter thereof was 3.59nm as obtained by scanning with a transmission electron microscope (see FIG. 1).
The application of the palladium catalyst in the electro-synthesis of cinnamyl alcohol comprises the following steps:
1) 70mg of palladium catalyst and 2mmoL of cinnamaldehyde were dispersed in 20mL of catholyte, volume ratio of 1:1, 0.1mol/L neutral potassium phosphate aqueous solution and acetonitrile;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anolyte tank;
3) Working electrodes (1cm. Times.4cm Ti mesh electrodes) were inserted into the liquid in the cathodic electrolysis cell, and auxiliary electrodes (1cm. Times.1cm Pt sheet electrodes) were inserted into the anolyte (20mL 0.025mol/L H 2 SO 4 Aqueous solution), electrifying and reacting to obtain cinnamyl alcohol. Current of currentThe reaction mixture was electrified at 60mA for 3 hours.
Ethyl acetate half the volume of the reaction solution is added into the electrified reaction solution for extraction, the extracted upper layer liquid is taken for qualitative and quantitative detection by a gas chromatograph, test results are obtained, the Faraday efficiency and the selectivity of the product can be calculated, and the results are shown in figure 4. The faradic efficiency of the total product of the example reaches 66.16%, and the selectivity of cinnamyl alcohol is 74.2%.
Example 2
A preparation method of a palladium catalyst comprises the following steps:
1) Adding sodium chloropalladate into 100mg/L tin oxide water dispersion liquid, and stirring for 8 hours; the mass ratio of the sodium chloropalladate to the tin oxide is 1:3;
2) Adding 8.5mL of 0.8mg/mL dimethylamine borane aqueous solution into 200mL of the mixed solution obtained in the step 1), reacting for 30h, separating out precipitate, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst, wherein the average particle size of the palladium catalyst is 4.14nm by scanning through a transmission electron microscope (see figure 2).
The application of the palladium catalyst in the electro-synthesis of cinnamyl alcohol comprises the following steps:
1) 30mg of palladium catalyst and 0.8mmoL of cinnamaldehyde were dispersed in 20mL of catholyte, which was a mixture of 1:
1.5 of a mixed solution of a neutral potassium phosphate aqueous solution with the concentration of 0.05mol/L and acetonitrile;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anolyte tank;
3) Working electrodes (1cm. Times.4cm Ti mesh electrodes) were inserted into the liquid in the catholyte cell, and auxiliary electrodes (1cm. Times.1cm Pt sheet electrodes) were inserted into the anolyte (20mL 0.075mol/L H 2 SO 4 Aqueous solution), electrifying and reacting to obtain cinnamyl alcohol. The energization current was 50mA, and the energization reaction was carried out for 2 hours.
Ethyl acetate half the volume of the reaction solution is added into the electrified reaction solution for extraction, the extracted upper layer liquid is taken for qualitative and quantitative detection by a gas chromatograph, test results are obtained, the Faraday efficiency and the selectivity of the product can be calculated, and the results are shown in figure 4. The faradaic efficiency of the total product of the example reaches 39.67%, and the selectivity of the cinnamyl alcohol is 62.5%.
Example 3
A preparation method of a palladium catalyst comprises the following steps:
1) Adding sodium chloropalladate into the tin oxide water dispersion liquid with the concentration of 150mg/L, and stirring for 9 hours; the mass ratio of the sodium chloropalladate to the tin oxide is 1:6;
2) Adding 10mL of 0.5mg/mL dimethylamine borane aqueous solution into 200mL of the mixed solution obtained in the step 1), reacting for 24h, separating out precipitate, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst, wherein the average particle size of palladium is 3.46m by scanning through a transmission electron microscope (see figure 3).
The application of the palladium catalyst in the electro-synthesis of cinnamyl alcohol comprises the following steps:
1) 50mg of palladium catalyst and 1mmoL of cinnamaldehyde were dispersed in 20mL of catholyte, volume ratio of 1:
1, 0.1mol/L of neutral potassium phosphate aqueous solution and acetonitrile;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anode electrolytic cell;
3) Working electrodes (1cm. Times.4cm Ti mesh electrodes) were inserted into the liquid in the catholyte cell, and auxiliary electrodes (1cm. Times.1cm Pt sheet electrodes) were inserted into the anolyte (20mL of 0.05mol/L in H form) 2 SO 4 Aqueous solution), electrifying and reacting to obtain cinnamyl alcohol. The energization current was 40mA, and the energization reaction was carried out for 3 hours.
Ethyl acetate half the volume of the reaction solution is added into the electrified reaction solution for extraction, the extracted upper layer liquid is taken for qualitative and quantitative detection by a gas chromatograph, test results are obtained, the Faraday efficiency and the selectivity of the product can be calculated, and the results are shown in figure 4. The faradic efficiency of the total product in the example reaches 48.44%, and the selectivity of cinnamyl alcohol is 77.17%.
Comparative example 1
The application of commercial 5wt% palladium carbon in cinnamyl alcohol electrosynthesis comprises the following steps:
1) 50mg of commercial 5wt% palladium on carbon and 1mmoL of cinnamaldehyde were dispersed in 20mL of catholyte in a volume ratio of 1:1, 0.1mol/L of neutral potassium phosphate aqueous solution and acetonitrile;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anolyte tank;
3) Working electrodes (1cm. Times.4cm Ti mesh electrodes) were inserted into the liquid in the catholyte cell, and auxiliary electrodes (1cm. Times.1cm Pt sheet electrodes) were inserted into the anolyte (20mL 0.05mol/L H 2 SO 4 Aqueous solution), electrifying and reacting to obtain cinnamyl alcohol. The energization current was 40mA, and the energization reaction was carried out for 3 hours.
Ethyl acetate half the volume of the reaction solution is added into the electrified reaction solution for extraction, the extracted upper layer liquid is taken for qualitative and quantitative detection by a gas chromatograph, test results are obtained, the Faraday efficiency and the selectivity of the product can be calculated, and the results are shown in figure 4. The faradaic efficiency of the total product of the comparative example reaches 30.93 percent, and the selectivity of the cinnamyl alcohol is 30.85 percent.
As can be seen from fig. 4, the catalyst of the present invention has higher selectivity and does not produce dimer impurities, compared to other catalysts.
Claims (10)
1. A preparation method of a palladium catalyst is characterized by comprising the following steps:
1) Adding chloropalladate into 100-200mg/L tin oxide water dispersion liquid, and stirring for 8-12 h; the mass ratio of the chloropalladate to the tin oxide is 1 (3-6);
2) Adding 8.5-17mL of dimethylamine borane aqueous solution with the concentration of 0.4-0.8 mg/mL into 200mL of the mixed solution obtained in the step 1) according to the volume ratio, reacting for 12-30 h, separating out precipitates, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the palladium catalyst.
2. The method according to claim 1, wherein the stirring time in step 1) is 9 hours.
3. The method of claim 1, wherein the chloropalladate is sodium or potassium chloropalladate.
4. A palladium catalyst prepared by the process of any one of claims 1 to 3.
5. Use of a palladium catalyst according to claim 4 in the electrosynthesis of cinnamyl alcohol.
6. The use of a palladium catalyst in the electrosynthesis of cinnamyl alcohol as defined in claim 5, including the steps of:
1) Dispersing 30-70 mg of palladium catalyst and 0.8-2 mmoL of cinnamaldehyde in 20mL of cathode electrolyte according to the proportion;
2) Adding the liquid obtained in the step 1) into a cathode electrolytic cell of an H-shaped electrolytic cell separated by a proton exchange membrane Nafion 117; adding 20mL of anolyte into the anode electrolytic cell;
3) And inserting the working electrode into the liquid in the cathode electrolytic cell, inserting the auxiliary electrode into the anolyte, electrifying, and reacting to obtain the cinnamyl alcohol.
7. The use according to claim 6, wherein the catholyte is present in a volume ratio of 1: (1-1.5) a mixture of a neutral potassium phosphate aqueous solution having a concentration of 0.05-0.1 mol/L and acetonitrile.
8. The use according to claim 6, wherein the anolyte is 0.025 to 0.075mol/L H 2 SO 4 An aqueous solution.
9. The use according to claim 6, wherein the working electrode is a Ti mesh electrode; the auxiliary electrode is a Pt sheet electrode.
10. The use according to claim 6, wherein the step (3) is performed by applying a current of 40-60 mA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110769051.0A CN115595625A (en) | 2021-07-07 | 2021-07-07 | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110769051.0A CN115595625A (en) | 2021-07-07 | 2021-07-07 | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115595625A true CN115595625A (en) | 2023-01-13 |
Family
ID=84840738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110769051.0A Pending CN115595625A (en) | 2021-07-07 | 2021-07-07 | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115595625A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000033266A (en) * | 1998-07-16 | 2000-02-02 | Osaka Gas Co Ltd | Catalyst for purifying hydrocarbon-containing exhaust gas and purification of hydrocarbon-containing exhaust gas |
| CN101703930A (en) * | 2009-11-30 | 2010-05-12 | 葛昌华 | Palladium/carbon nanotube catalyst for hydrogenation of cinnamaldehyde and preparation method thereof |
| CN105537619A (en) * | 2015-12-29 | 2016-05-04 | 天津大学 | Palladium nano-particles with peroxidase activity and preparation method thereof |
| CN111450831A (en) * | 2020-05-22 | 2020-07-28 | 北京化工大学 | High-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and preparation method thereof |
-
2021
- 2021-07-07 CN CN202110769051.0A patent/CN115595625A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000033266A (en) * | 1998-07-16 | 2000-02-02 | Osaka Gas Co Ltd | Catalyst for purifying hydrocarbon-containing exhaust gas and purification of hydrocarbon-containing exhaust gas |
| CN101703930A (en) * | 2009-11-30 | 2010-05-12 | 葛昌华 | Palladium/carbon nanotube catalyst for hydrogenation of cinnamaldehyde and preparation method thereof |
| CN105537619A (en) * | 2015-12-29 | 2016-05-04 | 天津大学 | Palladium nano-particles with peroxidase activity and preparation method thereof |
| CN111450831A (en) * | 2020-05-22 | 2020-07-28 | 北京化工大学 | High-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QIANQIAN ZHANG ET AL.: "Highly selective electrocatalytic hydrogenation of cinnamaldehyde over tin dioxide-supported palladium nanocatalysts", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 47, no. 90, 22 September 2022 (2022-09-22), pages 38229 - 38241 * |
| 吴以保等: "纳米催化剂Pd/SnO2的制备及催化还原硝酸盐反应的调控", 环境科学学报, vol. 30, no. 12, 31 December 2010 (2010-12-31), pages 2464 - 2470 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Enhance CO2-to-C2+ products yield through spatial management of CO transport in Cu/ZnO tandem electrodes | |
| CN108660479B (en) | Method for preparing KA oil and derivatives thereof through electrocatalytic hydrogenation of lignin-based phenolic compounds | |
| CN113388853B (en) | Electrochemical catalysis method for highly selective hydrogenation of carbon-carbon triple bonds | |
| Zhao et al. | Electrocatalytic hydrogenation of lignin-derived phenol into alkanes by using platinum supported on graphite | |
| CN114277398B (en) | Preparation method and application of nano copper catalyst | |
| CN111013615A (en) | Preparation method of CoP catalyst with hydrogen precipitation and oxygen precipitation high-efficiency dual functions | |
| Moutet | Electrocatalytic hydrogenation on hydrogen-active electrodes. A review | |
| CN111215146B (en) | Group-modified noble metal-based carbon dioxide electro-reduction catalyst and preparation method and application thereof | |
| CN110227513A (en) | A kind of carbon-based carried metal phosphide catalyst and its preparation method and application | |
| CN112609201A (en) | Method for pair-wise synthesizing carbonic diester and sebacic diester | |
| CN113373464B (en) | Method for preparing cyclane by electrocatalytic conversion of lignin derivative | |
| Lee et al. | Selective electroreduction of glycerol to 1, 2-propanediol on a mixed carbon-black activated carbon electrode and a mixed carbon black-diamond electrode | |
| US20040053098A1 (en) | Electrochemical cell | |
| CN115595625A (en) | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis | |
| Gao et al. | Tuning electrochemical environment enables unexpected C= O selectivity for cinnamaldehyde hydrogenation over self-standing palladium cathode | |
| Lima et al. | CO2 reduction on Cu/C used as a cathode in a polymeric electrolyte reactor-Fuel cell type | |
| CN113502489B (en) | Preparation method and application of electrocatalyst for reduction of alkyne into olefin | |
| EP4015673A1 (en) | Electrocatalytic oxidation of alcohols using acceptor-less dehydrogenation catalysts | |
| CN114836781A (en) | Preparation method and application of lamellar Cu-based N-doped graphene catalyst | |
| Youn et al. | Carbon-supported PtPb intermetallic compounds for electrooxidation of methyl formate | |
| Deronzier et al. | Polymers of Platinum Metals Complexes Immobilised on Electrodes | |
| Pu et al. | Surface coating combined with in situ cyclic voltammetry to enhance the stability of gas diffusion electrodes for electrochemical CO2 reduction | |
| Atobe et al. | Organic electrosynthetic processes using solid polymer electrolyte reactor | |
| Angizi et al. | Toward valorization of crude glycerol via controlled electro-oxidation | |
| CN115029751B (en) | Pt/MoS 2 Electroplating preparation method of nano-sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |