CN115125574A - Method for connecting carbon-based electrocatalyst and TS-1 thermal catalyst in series and application of carbon-based electrocatalyst and TS-1 thermal catalyst in-situ preparation of propylene oxide by electrocatalytic oxygen reduction - Google Patents
Method for connecting carbon-based electrocatalyst and TS-1 thermal catalyst in series and application of carbon-based electrocatalyst and TS-1 thermal catalyst in-situ preparation of propylene oxide by electrocatalytic oxygen reduction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 41
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 36
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-
- 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
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- 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
- C25B3/29—Coupling reactions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series and application thereof in-situ preparation of propylene oxide by electrocatalytic oxygen reduction. On the cathode side, the carbon-based electrocatalyst is used for reducing oxygen to produce H 2 O 2 The catalyst, carbon-based electrocatalyst and thermal catalyst TS-1 are connected in series and cooperatively used as a cathode side catalyst; simultaneously, oxygen and propylene are introduced into the cathode side, and the oxygen is firstly reduced to generate H under the action of a carbon-based electrocatalyst 2 O 2 (ii) a Subsequent generation of H 2 O 2 In combination with TS-1 on the cathode side, propylene oxide is prepared by in situ epoxidation of propylene. The invention relates to a carbon-based electrocatalyst and TS-1In series, and reduction of oxygen to H 2 O 2 Coupled with propylene epoxidation reaction to realize H generated by oxygen reduction 2 O 2 The propylene epoxide is prepared by in-situ catalyzing the epoxidation of the propylene, and the yield of the propylene epoxide in a flowing electrolysis cell reaches 11.68mmol g cat ‑1 h ‑1 (ii) a Preparing high-activity and high-selectivity transition metal monoatomic doped mesoporous carbon to ensure that H is 2 O 2 Selectivity can reach 94%, Faraday efficiency is close to 100%, H 2 O 2 The yield reaches 519 mmoleg cat ‑1 h ‑1 。
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and relates to a method for connecting a carbon-based electrocatalyst and a TS-1 thermocatalyst in series and application thereof in-situ preparation of propylene oxide by electrocatalytic oxygen reduction.
Background
Propylene oxide is one of the most important raw materials in the plastics industry for the production of bulk chemicals such as polyurethane, polyester fiber and propylene glycol. In industry, propylene oxide is generally produced by a chlorohydrin method and an oxidation method, and although the propylene oxide has the advantages of low product cost and the like, the propylene oxide still has the environmental risks of more byproducts, complicated process flows and the generation of a large amount of waste water and waste residues. In recent years, attention has been paid to a hydrogen peroxide direct oxidation method (HPPO method) using hydrogen peroxide (H) 2 O 2 ) The titanium silicalite TS-1 is used as an oxidant and used as a catalyst to catalyze epoxidation of propylene to prepare propylene oxide, only propylene oxide and water are generated in the production process, the process flow is simple, the propylene oxide yield is high, and the environment-friendly effect is achieved. However, the oxidizing agent H 2 O 2 The large-scale production mainly adopts a multistep anthraquinone process, has large energy consumption and more organic wastes, is difficult to produce on site and has high concentration H 2 O 2 High costs and high risks exist for storage and transportation of (2). Therefore, in order to avoid or solve the above problems, the HPPO method needs further development.
In recent years, electrocatalytic oxygen reduction (ORR) synthesis of H via a two electron transfer process 2 O 2 Has attracted a great deal of attention in both academic and industrial circles. Compared with the traditional anthraquinone process, the method has the advantages of mild reaction conditionsRenewable electric power driven CO emission free 2 And air and water are used as reaction raw materials, so that the method is more in line with the requirements of green chemical industry. In electrocatalytic ORR, electrocatalysts are the key to the reaction. Currently, noble metals are electrocatalytic ORR producing H 2 O 2 Electrocatalysts of optimal performance, but the expensive price, scarcity and poor tolerance of noble metals to acidic and basic environments limit the possibilities for their practical application. However, carbon materials have received increasing attention due to their large specific surface area, abundant resources, acid and alkali resistance, and high electrical conductivity, and are considered as promising and potential precious metal substitutes. However, the electrocatalytic activity of pure carbon-based catalysts is generally low, and modification of the carbon material is required to increase the catalytic activity. ORR Activity and H of carbon-based catalysts in the prior art 2 O 2 The selectivity is yet to be further improved.
Disclosure of Invention
Aiming at the problems, the invention aims to realize the in-situ preparation of the propylene oxide by electrocatalytic oxygen reduction, explores the series connection of an electrocatalyst and a thermal catalyst and the coupling engineering of the electrocatalytic reaction and the thermal catalytic reaction, and reduces the H generated in situ by the oxygen 2 O 2 The method is applied to producing propylene oxide by propylene epoxidation, and in addition, the invention also prepares high-activity and high-selectivity oxygen reduction H 2 O 2 The carbon-based catalyst of (1).
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series comprises the steps of coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on one side of a cathode current collector in sequence according to different sequences, or coating the carbon-based catalyst and the TS-1 thermal catalyst on one side of the cathode current collector after uniformly mixing to obtain an electrode plate with the catalyst covered on one side.
The TS-1 thermal catalyst and the carbon-based electrocatalyst are coated on one side of a cathode current collector in sequence according to different sequences, the method comprises the steps of coating the carbon-based electrocatalyst on one side of the cathode current collector and coating the TS-1 thermal catalyst on the surface of the carbon-based electrocatalyst, and preferably, the area of the TS-1 thermal catalyst is smaller than that of the carbon-based electrocatalystFurther, the area of the carbon-based electrocatalyst is 0.5 x 1-1.5 x 1cm 2 The TS-1 thermal catalyst has an area of 0.25 x 1 to 1 x 1cm 2 (ii) a Or coating TS-1 thermal catalyst on one side of the cathode current collector, and coating carbon-based electrocatalyst on the surface of the TS-1 thermal catalyst.
A method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series comprises the steps of uniformly mixing the carbon-based electrocatalyst and the TS-1 thermal catalyst and then coating the mixture on two sides of a cathode current collector, or sequentially coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on two sides of the cathode current collector according to different sequences, or respectively coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of the cathode current collector to obtain electrode plates with catalysts covered on two sides.
The carbon-based electrocatalyst and the TS-1 thermal catalyst are sequentially coated on two sides of a cathode current collector in different sequences, the carbon-based electrocatalyst is coated on two sides of the cathode current collector, then the TS-1 thermal catalyst is coated on the surface of the carbon-based electrocatalyst, preferably, the area of the TS-1 thermal catalyst on each side of the cathode current collector is smaller than that of the carbon-based electrocatalyst, and further, the area of the carbon-based electrocatalyst on each side of the cathode current collector is 0.5 x 1-1.5 x 1cm 2 The TS-1 thermal catalyst has an area of 0.25 x 1 to 1 x 1cm 2 (ii) a Or coating TS-1 thermal catalyst on two sides of the cathode current collector, and then coating carbon-based electrocatalyst on the surface of the TS-1 thermal catalyst.
The mass ratio of the carbon-based electrocatalyst to the TS-1 thermocatalyst is 0.5:1-1: 10; when the carbon-based catalyst is mixed with the TS-1 thermal catalyst, the mass ratio of the carbon-based electrocatalyst to the TS-1 is preferably 1: 10.
The preparation method of the electrode plate with the catalyst covered on one side comprises the following steps: independently dispersing a carbon-based electrocatalyst and a TS-1 thermal catalyst in a mixed solvent of deionized water, ethanol and 5 wt% of Nafion solution, sequentially coating the mixture on one side of a cathode current collector in different orders, and drying, or mixing the carbon-based electrocatalyst and the TS-1 thermal catalyst, fully grinding, uniformly dispersing the mixture in a mixed solvent of deionized water, ethanol and 5 wt% of Nafion solution by ultrasonic to obtain uniform catalyst slurry, dripping the catalyst slurry on one side of the cathode current collector, and drying.
The preparation method of the electrode plate with the catalyst covered on both sides comprises the following steps: mixing a carbon-based electrocatalyst and a TS-1 thermal catalyst, fully grinding, uniformly dispersing in a mixed solvent of deionized water, ethanol and 5 wt% of Nafion solution by ultrasonic to obtain uniform catalyst slurry, dripping the catalyst slurry on two sides of a cathode current collector, and drying; or respectively dispersing the carbon-based electrocatalyst and the TS-1 thermal catalyst in a mixed solvent of deionized water, ethanol and 5 wt% of Nafion solution, sequentially coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of a cathode current collector in different orders or respectively coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of the cathode current collector, and drying.
The cathode current collector is carbon paper, carbon cloth or carbon felt.
The carbon-based electrocatalyst is a transition metal monoatomic-doped carbon-based electrocatalyst.
The preparation method of the transition metal monoatomic-doped carbon-based electrocatalyst comprises the following steps of:
s1, preparing a salt solution of transition metal M, dispersing the solution into SBA-15 solid powder by an equal volume impregnation method, drying and adding H 2 Carrying out hydrogen reduction in an/Ar atmosphere to obtain a sample of SBA-15 loaded transition metal particles, and marking the sample as M/SBA-15;
s2, taking M/SBA-15 as a template, taking a carbon source solution to be dipped into the M/SBA-15 solid powder in an equal volume, aging and polymerizing, and calcining in Ar atmosphere;
and S3, performing alkali washing on the obtained black solid powder by using an aqueous sodium hydroxide solution to remove the SBA-15 template, and performing acid washing by using a hydrochloric acid solution to remove the transition metal particles to obtain the transition metal monoatomic-doped carbon-based electrocatalyst.
In step S1, the transition metal M salt includes at least one of ferric chloride, cobalt chloride, nickel chloride, manganous chloride, and cupric chloride; preferably, the transition metal M salt is cobalt chloride hexahydrate. The theoretical loading of cobalt is 1-50 wt.%, preferably the theoretical loading of cobalt is 17.38 wt.%.
In step S1, the hydrogen reduction temperature is 250-.
The carbon source solution in the step S2 is a mixture of furfuryl alcohol, trimethylbenzene and oxalic acid, wherein the ratio of furfuryl alcohol, trimethylbenzene and oxalic acid is 0-2:0-2:10-30(ml: ml: mg), and preferably the ratio of furfuryl alcohol, trimethylbenzene and oxalic acid is 1:1:22.6(ml: ml: mg).
The calcination temperature in step S2 is 700-900 ℃, the calcination time is 2-5h, preferably, the calcination temperature is 850 ℃, and the calcination time is 4 h.
In step S3, the method for removing SBA-15 comprises washing in water bath in 0.5-2M NaOH water-alcohol solution, and V Ethanol ：V Water (I) The water bath temperature is 50 ℃, and the washing time is 24 h.
A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction comprises the following steps:
s1, obtaining an electrode plate with one side covered with a catalyst by the series connection method, and assembling a flow type electrolytic cell by taking the electrode plate as a cathode;
s2, adding electrolyte, and continuously introducing a mixed gas of oxygen and propylene to the cathode side to saturate the cathode;
s3, adopting a constant potential mode, and continuously electrolyzing at each potential.
The TS-1 thermal catalyst is distributed at one end of the gas outlet.
The cathode current collector in step S1 is a hydrophobic carbon paper containing a gas diffusion layer.
A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction comprises the following steps:
s1, assembling an H-shaped electrolytic cell by taking the electrode plates of the double-side covered catalyst obtained by the series connection method as cathodes;
s2, adding electrolyte, and continuously introducing a mixed gas of oxygen and propylene to the cathode side to saturate the mixed gas;
s3, adopting constant potential mode, each potential continuously electrolyzing.
The electrode plate with the catalyst covered on the two sides is obtained by respectively coating a carbon-based electrocatalyst and a TS-1 thermal catalyst on the two sides of a cathode current collector.
The electrolyte in the flow type electrolytic cell and the H type electrolytic cell is 0.1M sodium phosphate buffer solution with the pH value of 6, the flow rate of the electrolyte is 45rpm, the flow rate of propylene is 6.5sccm, and the flow rate of oxygen is 8.9 sccm.
The reduction potential in the flow-type electrolytic cell and the H-type electrolytic cell is 0-0.7V vs. RHE, preferably the reduction potential is 0.16V vs. RHE.
And the carbon-based electro-catalyst in the electrode plates of the flow type electrolytic cell and the H-shaped electrolytic cell is contacted with the electrolyte.
Compared with the prior art, the invention has the following outstanding characteristics:
1. the transition metal monoatomic-doped mesoporous carbon-based electrocatalyst prepared by the invention has excellent oxygen reduction H production 2 O 2 Performance, H 2 O 2 Selectivity can reach 94%, Faraday efficiency is close to 100%, H 2 O 2 The yield reaches 519mmol g cat -1 h -1 RHE, at 0.2V vs. up to 50mA cm in kinetic current density -2 The mesoporous structure can obviously improve the diffusion and mass transfer of reactants and electrolyte ions, thereby enhancing the reaction kinetics and improving the current density.
2. The invention realizes the simultaneous series coupling engineering of catalyst and reaction, namely the production of H by oxygen reduction 2 O 2 Electrocatalyst and propylene epoxidation thermal catalyst in series and oxygen reduction to produce H 2 O 2 The reaction is coupled with the epoxidation reaction of propylene, and H is produced by oxygen reduction 2 O 2 The cooperation of the electrocatalyst and the propylene epoxidation thermal catalyst as a cathode side catalyst realizes the in-situ preparation of propylene oxide by electrocatalytic oxygen reduction, and the preparation is similar to the conventional H 2 O 2 Compared with the production process for producing the epoxypropane by the direct oxidation method, the method has the advantages of mild reaction conditions, easy control of the reaction, low energy consumption and avoidance of H 2 O 2 The separation, storage, transportation and the like, and has wide application prospect.
3. The yield of the propylene oxide prepared by the electrocatalytic oxygen reduction in situ method in the flowing electrolytic cell reaches 11.68mmol g cat -1 h -1 (wherein each gram of catalyst refers to each gram of carbon-based electrocatalyst); propylene oxide product prepared by electrocatalytic oxygen reduction in situ process in H-cellThe amount of 9mmol g cat -1 h -1 (wherein each gram of catalyst refers to each gram of carbon-based electrocatalyst). Direct series connection of TS-1 with an electrocatalyst can shorten H compared to TS-1 dispersed in electrolyte 2 O 2 The diffusion distance to the surface of TS-1, thereby accelerating the reaction rate and improving the utilization rate of TS-1 and the yield of propylene oxide.
Drawings
FIG. 1 is a graph of isothermal nitrogen adsorption-desorption curves for Co-O-C, with the inset showing the pore size distribution;
FIG. 2 is a wide angle XRD pattern of Co-O-C;
FIG. 3 is a LSV plot of Co-O-C and a comparative O-C;
FIG. 4 is H for Co-O-C and comparative O-C 2 O 2 A selectivity profile;
FIG. 5 is H of Co-O-C 2 O 2 A Faraday efficiency map;
FIG. 6 is H of Co-O-C 2 O 2 A yield map;
FIG. 7 is a graph showing propylene oxide yields for different series arrangements of Co-O-C and TS-1;
FIG. 8 is the chromatogram of the reaction product after optimal conditions;
FIG. 9 is a diagram showing the analysis of the chromatographic product of TS-1 dispersed in an electrode solution;
FIG. 10 is a schematic view of a flow cell cathode;
FIG. 11 is a chromatogram of the electrolyte in a flow cell.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments in order to explain technical contents, objects, and effects of the invention in detail.
Example 1
The preparation method of the transition metal cobalt monoatomic doped carbon-based electrocatalyst comprises the following specific steps:
(1) weighing 0.8172g of cobalt chloride hexahydrate in 2ml of deionized water at room temperature, ultrasonically dissolving, taking 500 mu l of the solution by an equal-volume impregnation method, dispersing into 0.5g of SBA-15 solid powder, rapidly stirring and extruding to obtain light pink powder, transferring the powder into a 50 ℃ oven for overnight dryingDrying to dry the water, then hydrogen reduction, in H 2 Calcining for 2H at 450 ℃ in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃/min, and H 2 The flow of (A) was 6.5ml/min and the flow of Ar was 74.9ml/min, and brick red solid powder was obtained after calcination and was noted as Co/SBA-15.
(2) Taking Co/SBA-15 in the step (1) as a template, taking 900 mu l of carbon source solution (4ml of furfuryl alcohol, 4ml of trimethylbenzene, 90.5mg of oxalic acid and ultrasonic dissolution of the oxalic acid), soaking the carbon source solution into Co/SBA-15 solid powder in an equal volume according to the soaking method in the step (1), transferring the soaked sample into an oven for aging polymerization, wherein the aging procedure is 12 hours in a 50 ℃ oven, 12 hours in a 90 ℃ oven and 12 hours in an 80 ℃ oven, drying the sample in the oven in an open manner for 12 hours, and then putting the sample into a tubular furnace to be heated to 850 ℃ at the heating rate of 5 ℃/min and calcining for 4 hours in the Ar atmosphere.
(3) The calcined sample was first treated with 1.8M NaOH in hydroalcoholic solution (V) Ethanol ：V Water (W) 1:3) for 24h at 50 ℃ to remove template SBA-15. And (3) soaking the sample with the template removed at 50 ℃ for 24h by using 4M hydrochloric acid to remove the metal cobalt nanoparticles, then performing suction filtration and washing by using deionized water, and drying to obtain the cobalt monoatomic-doped carbon-based electrocatalyst, which is marked as Co-O-C.
FIG. 1 is a nitrogen adsorption-desorption isotherm graph of carbon-based electrocatalyst Co-O-C; as can be seen from the nitrogen adsorption figure, the catalyst Co-O-C is of a mesoporous structure, and the pore size distribution is concentrated at 3.0 nm.
FIG. 2 is a wide angle XRD pattern of Co-O-C; according to a wide-angle XRD pattern, the catalyst Co-O-C is an amorphous carbon material, and no obvious diffraction peak of metal particles exists in the XRD pattern, which shows that the metal cobalt is distributed in the Co-O-C in an atomic form.
Comparative example 1 (not according to the invention)
The preparation of a comparative pure carbon material was carried out according to the step (2) in example 1, except that SBA-15 was used as a carbon source template and was marked as O-C.
Example 2
Application of carbon-based electrocatalyst Co-O-C in example 1 and O-C in comparative example 1 to electrocatalytic oxygen reduction of H 2 O 2 The performance test comprises the following specific steps:
ORR Activity and selectionThe selective test uses a Rotating Ring Disk Electrode (RRDE), and a four-electrode system is established by taking RRDE (glass carbon disk + Pt ring) as a working electrode, a saturated Ag/AgCl reference electrode and a platinum wire counter electrode. Respectively weighing 6.2mg Co-O-C and 6.2mg O-C, ultrasonically dispersing in 1ml mixed solution consisting of 5 wt.% of 50ul Nafion, 665ul deionized water and 285ul ethanol, transferring 6 mu l of electrocatalyst serous fluid water drop by using a liquid transfer gun to be coated on the surface of a glassy carbon disk of a ring disk electrode, naturally drying at room temperature, and preparing a working electrode for oxygen reduction activity and selectivity test, wherein the catalyst loading amount is 0.3mg cm -2 。
H 2 O 2 The productivity test adopts an H-type electrolytic cell, and a three-electrode system is assembled by taking carbon paper coated with an ordered cathode mesoporous carbon catalyst as a cathode, a platinum sheet as an anode and saturated Ag/AgCl as a reference electrode. 80 mul of the catalyst slurry is dripped and coated on two sides of carbon paper, and the catalyst loading capacity is 0.50mg cm -2 . Oxygen was continuously fed to the cathode side at a flow rate of 40ml min -1 . Electrolyzing by constant potential method, wherein each potential is continuously electrolyzed for 7200 s; adopts cerium sulfate as a calibration agent and combines ultraviolet spectrum with H in catholyte 2 O 2 The content was quantified.
FIG. 3 is a LSV plot of Co-O-C and a comparative O-C; as can be seen from the LSV graph, the catalysts Co-O-C and O-C both have oxygen reduction activity, the O-C disk current is higher than that of Co-O-C, and the ring current of Co-O-C is higher than that of O-C.
FIG. 4 is H for Co-O-C and comparative O-C 2 O 2 A selectivity profile; from H 2 O 2 The selectivity is known, the selectivity of the catalyst Co-O-C is higher than H of O-C and Co-O-C in the test potential range 2 O 2 The selectivity can reach 93 percent at most.
FIG. 5 is H of Co-O-C 2 O 2 A Faraday efficiency map; as can be seen from FIG. 7, the Faraday efficiency of the catalyst Co-O-C approaches 100% over a wide potential range.
FIG. 6 is H of Co-O-C 2 O 2 A yield map; as can be seen from FIG. 8, H of Co-O-C catalyst 2 O 2 Yield increased with increasing voltage, up to 519mmol g at 0.4V vs. RHE potential cat -1 h -1 。
Example 3
The carbon-based catalyst Co-O-C and the TS-1 catalyst are connected in series and applied to oxygen reduction in-situ preparation of propylene oxide, and the method comprises the following specific steps:
the series propylene epoxidation test adopts an H-type electrolytic cell, carbon paper coated with a carbon-based electrocatalyst and a TS-1 catalyst is used as a cathode, a platinum sheet is used as an anode, and saturated Ag/AgCl is used as a reference electrode to assemble a three-electrode system. Dripping TS-1 thermal catalyst slurry and Co-O-C electrocatalyst slurry with certain volume on two sides of carbon paper, and continuously introducing mixed gas of oxygen and propylene to cathode side at flow rates of 15ml min -1 . Electrolyzing by a potentiostatic method for 3 hours at each potential; adopts cerium sulfate as a calibration agent and combines ultraviolet spectrum with H in catholyte 2 O 2 The content was determined, and the content of propylene oxide in the catholyte was determined by gas chromatography.
The quality of the carbon-based electrocatalyst and the quality of the TS-1 thermocatalyst on the electrode sheet which are prepared in different series connection modes are respectively as follows:
respectively coating a carbon-based catalyst and a TS-1 thermal catalyst on two sides of carbon paper: carbon-based catalyst 0.45mg, TS-1 thermal catalyst 0.9 mg;
carbon-based electrocatalyst covers TS-1 thermal catalyst on both sides of carbon paper: carbon-based catalyst 1.2mg, TS-1 thermal catalyst 2.4 mg;
the carbon-based catalyst and the TS-1 thermal catalyst are mixed and coated on two sides of the carbon paper: 3.6mg of carbon-based catalyst and 30.6mg of TS-1 thermal catalyst.
The working area of the electrode plates manufactured in different series connection modes is 1 x 1cm 2 。
FIG. 7 is a comparison of epoxy yields under different conditions during the search, and it can be seen from FIG. 7 that the yields are highest when two catalysts are drop-coated on both sides of the carbon paper, respectively.
FIG. 8 is a chromatogram of the product after reaction under optimal conditions; as can be seen from FIG. 8, the yield of propylene oxide of the series catalyst was up to 9mmol g cat -1 h -1 。
Comparative example 2 (not according to the invention)
The carbon-based catalyst Co-O-C oxygen reduction is used for preparing hydrogen peroxide and the TS-1 catalyst dispersed in the electrolyte is used for preparing propylene oxide by epoxidizing propylene, and the specific steps are as follows:
the series propylene epoxidation test adopts an H-shaped electrolytic cell, takes carbon-based electro-catalysis as a cathode, 0.45mg of carbon-based catalyst and 1 x 1cm of working area 2 The platinum sheet is used as an anode, and the saturated Ag/AgCl is used as a reference electrode to assemble a three-electrode system. Dispersing 0.9mg TS-1 in the cathode electrolyte, and continuously introducing mixed gas of oxygen and propylene into the cathode side at flow rates of 15ml min -1 . Electrolyzing by a potentiostatic method for 3 hours at each potential; adopts cerium sulfate as a calibration agent and combines ultraviolet spectrum with H in catholyte 2 O 2 The content was determined, and the content of propylene oxide in the catholyte was determined by gas chromatography.
No propylene oxide product was detected.
FIG. 9 is an analysis chart of a chromatographic product obtained by dispersing TS-1 in an electrode solution.
Example 4
A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction comprises the following specific steps:
the series propylene epoxidation test uses a flow electrolytic cell, and a three-electrode system is assembled by using hydrophobic carbon paper coated with a carbon-based electrocatalyst and a TS-1 thermal catalyst and containing a gas diffusion layer as a cathode, a platinum sheet as an anode and saturated Ag/AgCl as a reference electrode. 350 μ l of the Co-O-C electrocatalyst ink of example 2 was applied in drops onto carbon paper with a working area of 1 x 1cm 2 After drying, TS-1 thermal catalyst slurry is dripped on the surface of the Co-O-C electrocatalyst, and the working area is 0.5 x 1cm 2 Wherein the TS-1 catalyst is distributed at one end of the air outlet, the TS-1 thermal catalyst loading capacity is 2mg cm -2 The Co-O-C electrocatalyst loading is 1mg cm -2 . Continuously introducing mixed gas of oxygen and propylene to the cathode side at oxygen flow rate of 15ml min -1 Propylene flow rate of 15ml min -1 . Electrolyzing by a potentiostatic method for 3 hours at each potential; adopts cerium sulfate as a calibration agent and combines ultraviolet spectrum with H in catholyte 2 O 2 The content was determined, and the content of propylene oxide in the catholyte was determined by gas chromatography.
FIG. 10 is a schematic view of a flow cell cathode; it shows that TS-1 thermal catalyst is coated on the surface of the carbon-based electrocatalyst, and the coating area accounts for half of the current collector.
FIG. 11 is a chromatogram of the electrolyte in a flow cell, and it can be seen from FIG. 11 that the yield of propylene oxide in the in situ hydrogen peroxide epoxidation reaction in the flow cell is up to 11.68mmol g cat -1 h -1 。
Claims (9)
1. A method for connecting a carbon-based electrocatalyst and a TS-1 thermocatalyst in series is characterized in that: the preparation method comprises the steps of coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on one side of a cathode current collector in sequence according to different sequences, or uniformly mixing the carbon-based catalyst and the TS-1 thermal catalyst and then coating the mixture on one side of the cathode current collector to obtain the electrode plate with the catalyst covered on one side.
2. A method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series is characterized in that: the method comprises the steps of uniformly mixing a carbon-based catalyst and a TS-1 thermal catalyst and then coating the mixture on two sides of a cathode current collector, or sequentially coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on two sides of the cathode current collector in different orders, or respectively coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of the cathode current collector to obtain the electrode plate with catalysts covered on two sides.
3. A process of carbon-based electrocatalyst and TS-1 thermocatalyst in series as claimed in claim 1 or 2 wherein: the mass ratio of the carbon-based electrocatalyst to the TS-1 thermal catalyst is 0.5:1-1: 10.
4. A process of carbon-based electrocatalyst and TS-1 thermocatalyst in series as claimed in claim 1 or 2 wherein: the cathode current collector is carbon paper, carbon cloth or carbon felt.
5. A process of carbon-based electrocatalyst and TS-1 thermocatalyst in series as claimed in claim 1 or 2 wherein: the carbon-based electrocatalyst is a transition metal single-atom doped carbon-based electrocatalyst.
6. A process according to claim 5, wherein the carbon-based electrocatalyst is connected in series with a TS-1 thermal catalyst, wherein: the preparation method of the transition metal monoatomic-doped carbon-based electrocatalyst comprises the following steps of:
s1, preparing a salt solution of transition metal M, dispersing the solution into SBA-15 solid powder by an equal volume impregnation method, drying and adding H 2 Carrying out hydrogen reduction in an/Ar atmosphere to obtain a sample of SBA-15 loaded transition metal particles, and marking the sample as M/SBA-15;
s2, taking M/SBA-15 as a template, taking a carbon source solution to be dipped into the M/SBA-15 solid powder in an equal volume, aging and polymerizing, and calcining in Ar atmosphere;
and S3, performing alkali washing on the obtained black solid powder by using an aqueous sodium hydroxide solution to remove the SBA-15 template, and performing acid washing by using a hydrochloric acid solution to remove the transition metal particles to obtain the transition metal monoatomic-doped carbon-based electrocatalyst.
7. A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction is characterized by comprising the following steps: the method comprises the following steps:
s1, assembling a flow type electrolytic cell by using the electrode sheet with the catalyst covered on one side obtained by the series connection method of claim 1 as a cathode;
s2, adding electrolyte, and continuously introducing a mixed gas of oxygen and propylene to the cathode side to saturate the mixed gas;
s3, adopting a constant potential mode, and continuously electrolyzing at each potential.
8. A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction is characterized by comprising the following steps: the method comprises the following steps:
s1, assembling an H-shaped electrolytic cell by taking the electrode plate of the double-side covered catalyst obtained by the series connection method of claim 2 as a cathode;
s2, adding electrolyte, and continuously introducing a mixed gas of oxygen and propylene to the cathode side to saturate the mixed gas;
s3, adopting a constant potential mode, and continuously electrolyzing at each potential.
9. The method for preparing propylene oxide in situ by electrocatalytic oxygen reduction as set forth in claim 7 or 8, wherein: the carbon-based electrocatalyst in the electrode plate is in contact with the electrolyte.
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| US20100234623A1 (en) * | 2009-03-13 | 2010-09-16 | Tokyo Metropolitan University | Method for producing propylene oxide |
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| US20100234623A1 (en) * | 2009-03-13 | 2010-09-16 | Tokyo Metropolitan University | Method for producing propylene oxide |
| CN103724299A (en) * | 2013-12-12 | 2014-04-16 | 中石化上海工程有限公司 | Method for preparing epoxy propane |
| CN103894227A (en) * | 2014-04-21 | 2014-07-02 | 厦门大学 | Preparation method of gold catalyst for preparing epoxypropane by virtue of propylene epoxidation |
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