CN115125574B - 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 preparing propylene oxide in situ through 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 preparing propylene oxide in situ through electrocatalytic oxygen reduction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000009467 reduction Effects 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims description 32
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- 239000004744 fabric Substances 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 abstract description 13
- 241000282326 Felis catus Species 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
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- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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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
-
- 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
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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)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series and application thereof in preparing propylene oxide in situ by electrocatalytic oxygen reduction. On the cathode side, the carbon-based electrocatalyst generates H for oxygen reduction 2 O 2 The catalyst, the carbon-based electrocatalyst and the thermal catalyst TS-1 are connected in series and cooperatively serve as a cathode side catalyst; simultaneously, oxygen and propylene are introduced into the cathode side, and the oxygen is reduced to generate H under the action of a carbon-based electrocatalyst firstly 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the H which is subsequently produced 2 O 2 And combining with TS-1 on the cathode side, and preparing propylene oxide by in-situ epoxidation of propylene. The invention connects the carbon-based electrocatalyst and TS-1 in series and reduces oxygen to prepare H 2 O 2 Coupled with propylene epoxidation reaction to realize H generated by oxygen reduction 2 O 2 In-situ catalytic epoxidation of propylene to propylene oxide with propylene oxide yield up to 11.68 mmolgs in a flow cell cat ‑1 h ‑1 The method comprises the steps of carrying out a first treatment on the surface of the Preparing high-activity and high-selectivity transition metal monoatomic doped mesoporous carbon to ensure H 2 O 2 The selectivity can reach 94%, the Faraday efficiency is close to 100%, H 2 O 2 The yield is up to 519 mmolgs 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 thermal catalyst in series and application of the carbon-based electrocatalyst and the TS-1 thermal catalyst in preparing propylene oxide in situ through 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 fibers and propylene glycol. In industry, propylene oxide is generally produced by a chlorohydrin method and a co-oxidation method, and has the advantages of low product cost and the like, but the production method still has the advantages of more byproducts, complicated process flow and environmental risk of generating a large amount of wastewater and waste residues. In recent years, a direct oxidation process of hydrogen peroxide (HPPO process) has been attracting attention, which uses hydrogen peroxide (H) 2 O 2 ) As an oxidant and a titanium silicalite molecular sieve TS-1 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 method is environment-friendly. However, oxidant H 2 O 2 The large-scale production of the catalyst mainly comprises a multi-step anthraquinone process, has large energy consumption and a large amount of organic wastes, is difficult to produce on site, and has high H concentration 2 O 2 There is a high cost, high risk for storage and transportation of (c). Therefore, to avoid or solve the above problems, the HPPO process needs further development.
In recent years, electrocatalytic oxygen reduction (ORR) reactions have synthesized H by a two electron transfer process 2 O 2 And has attracted considerable attention in academia and industry. Compared with the traditional anthraquinone process, the method has the advantages of mild reaction conditions and no CO emission due to renewable power 2 Air and water are used as reaction raw materials, so that the method meets the requirements of green chemical industry. In electrocatalytic ORR, the electrocatalyst is the key to the reaction. At present, noble metals are electrocatalytic ORR-produced H 2 O 2 Electrocatalysts with optimal performance, but the expensive price, scarcity and poor resistance to acidic and basic environments of noble metals limit the possibilities for practical use. However, carbon materials are receiving increasing attention due to their large specific surface area, abundant resources, acid and alkali resistance, and high conductivity, and are considered as promising and potential precious metal substitutes. However, the electrocatalytic activity of pure carbon-based catalysts is generally low, and the carbon material is requiredModification is performed to increase catalytic activity. ORR activity and H of carbon-based catalysts in the prior art 2 O 2 The selectivity is still to be further improved.
Disclosure of Invention
In view of the above problems, the present invention aims to provide in-situ preparation of propylene oxide by electrocatalytic oxygen reduction, and to explore the series connection of an electrocatalytic catalyst and a thermal catalyst and the coupling engineering of an electrocatalytic reaction and a thermal catalytic reaction, and to reduce in-situ generated H by oxygen 2 O 2 The method is applied to propylene epoxidation to produce propylene oxide, and in addition, the method also prepares high-activity and high-selectivity oxygeno-reduction H 2 O 2 Carbon-based catalyst of (a).
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for serially connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst 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 an electrode plate with a single-side covered catalyst.
The TS-1 thermal catalyst and the carbon-based electrocatalyst are coated on one side of the cathode current collector in sequence, comprising coating the carbon-based electrocatalyst on one side of the cathode current collector, coating the TS-1 thermal catalyst on the surface of the carbon-based electrocatalyst, preferably, the area of the TS-1 thermal catalyst is smaller than that of the carbon-based electrocatalyst, and further, the area of the carbon-based electrocatalyst is 0.5-1.5-1 cm 2 The area of the TS-1 thermal catalyst is 0.25 to 1cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Or coating a TS-1 thermal catalyst on one side of the cathode current collector, and coating a carbon-based electrocatalyst on the surface of the TS-1 thermal catalyst.
A method for serially connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst comprises the steps of uniformly mixing the carbon-based catalyst and the TS-1 thermal catalyst and then coating the mixture on two sides of a cathode current collector, or coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on two sides of the cathode current collector in different sequences, or coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of the cathode current collector respectively to obtain electrode plates with double-side covered catalysts.
The carbon-based electrocatalyst and the TS-1 thermal catalyst are coated on two sides of the cathode current collector in different sequences, comprising the steps of firstly coating the carbon-based electrocatalyst on two sides of the cathode current collector, and then coating the TS-1 thermal catalyst on the surface of the carbon-based electrocatalyst, wherein 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 area of the TS-1 thermal catalyst is 0.25 to 1cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Or firstly coating TS-1 hot catalyst on two sides of the cathode current collector, and then coating carbon-based electrocatalyst on the surface of the TS-1 hot catalyst.
The mass ratio of the carbon-based electrocatalyst to the TS-1 thermal catalyst is 0.5:1-1:10; when the carbon-based catalyst is mixed with the TS-1 thermal catalyst, preferably, the mass ratio of the carbon-based electrocatalyst to the TS-1 is 1:10.
The preparation method of the electrode slice with the catalyst covered on one side comprises the following steps: dispersing the carbon-based electrocatalyst and the TS-1 hot catalyst in a mixed solvent of deionized water, ethanol and 5wt% of Nafion solution, sequentially coating one side of a cathode current collector according to different sequences, drying, or mixing the carbon-based electrocatalyst and the TS-1 hot catalyst, fully grinding, uniformly dispersing in a mixed solvent of deionized water, ethanol and 5wt% of Nafion solution by ultrasonic, obtaining uniform catalyst slurry, coating the catalyst slurry on one side of the cathode current collector in a liquid drop manner, and drying.
The preparation method of the electrode slice with the catalyst covered on both sides comprises the following steps: mixing a carbon-based electrocatalyst with a TS-1 thermal catalyst, fully grinding, uniformly dispersing in a mixed solvent of deionized water, ethanol and 5wt% of Nafion solution by ultrasonic waves to obtain uniform catalyst slurry, then dripping the catalyst slurry on two sides of a cathode current collector, and drying; or respectively dispersing the carbon-based electrocatalyst and TS-1 thermal catalyst in a mixed solvent of deionized water, ethanol and 5wt% Nafion solution, sequentially coating the carbon-based electrocatalyst and TS-1 thermal catalyst on two sides of a cathode current collector or respectively coating the carbon-based electrocatalyst and TS-1 thermal catalyst on two sides of the cathode current collector according to different sequences, 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:
s1, preparing transition metal M salt water solution, dispersing the solution into SBA-15 solid powder by an isovolumetric impregnation method, drying and then adding the solution into H 2 Carrying out hydrogen reduction in Ar atmosphere to obtain a sample of SBA-15 loaded transition metal particles, which is designated as M/SBA-15;
s2, taking M/SBA-15 as a template, taking a carbon source solution to dip the carbon source solution into the M/SBA-15 solid powder in an equal volume, carrying out aging polymerization, and placing the mixture in Ar atmosphere for calcination;
s3, performing alkali washing on the obtained black solid powder by using a sodium hydroxide aqueous solution to remove the SBA-15 template, performing acid washing by using a hydrochloric acid solution to remove transition metal particles, and finally obtaining the transition metal single-atom doped carbon-based electrocatalyst.
In the step S1, the transition metal M salt comprises 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 1-50wt.%, preferably 17.38wt.%.
In the step S1, the hydrogen reduction temperature is 250-500 ℃, the reduction time is 0.5-2h, preferably, the hydrogen reduction temperature is 450 ℃, and the reduction time is 2h.
The carbon source solution in the step S2 is a mixed solution of furfuryl alcohol, trimethylbenzene and oxalic acid, wherein the ratio of furfuryl alcohol to trimethylbenzene to oxalic acid is 0-2:0-2:10-30 (ml: mg), and preferably the ratio of furfuryl alcohol to trimethylbenzene to oxalic acid is 1:1:22.6 (ml: mg).
The calcination temperature in step S2 is 700-900 ℃ and the calcination time is 2-5 hours, preferably 850 ℃ and the calcination time is 4 hours.
In the step S3, the SBA-15 is removed by water bath washing in 0.5-2M NaOH aqueous alcohol solution, V Ethanol ：V Water and its preparation method =1:3, water bath temperature of 50℃,The washing time was 24h.
A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction comprises the following steps:
s1, an electrode slice with a single side covered with a catalyst is obtained by the serial connection method and is used as a cathode to assemble a flow type electrolytic cell;
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 each potential.
The TS-1 thermal catalyst is distributed at one end of the air outlet.
In step S1, the cathode current collector 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, an H-shaped electrolytic cell is assembled by taking electrode plates with double sides covered with catalysts, which are obtained by the serial 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 a constant potential mode, and continuously electrolyzing each potential.
The electrode plates covered with the catalyst at both sides are obtained by respectively coating a carbon-based electrocatalyst and a TS-1 thermal catalyst on both sides of a cathode current collector.
The electrolyte in the flow cell and the H-cell was 0.1M sodium phosphate buffer solution with pH=6, the flow rate of the electrolyte was 45rpm, the flow rate of propylene was 6.5sccm, and the flow rate of oxygen was 8.9sccm.
The reduction potential in the flow cell and H cell is 0-0.7V vs. RHE, preferably 0.16V vs. RHE.
The carbon-based electrocatalyst in the electrode plates of the flow-type electrolytic cell and the H-type electrolytic cell is contacted with electrolyte.
Compared with the prior art, the invention has the following outstanding characteristics:
1. the transition metal single-atom doped mesoporous carbon-based electrocatalyst prepared by the invention has excellent oxygen reduction H production 2 O 2 Performance, H 2 O 2 The selectivity can reach 94%, the Faraday efficiency is close to 100%, H 2 O 2 Yield up to 519mmol g cat -1 h -1 At 0.2V vs. RHE, the kinetic current density is as high as 50mA cm -2 The mesoporous structure can obviously improve the diffusion and mass transfer of the reactant 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 The electrocatalyst is connected with propylene epoxidation thermal catalyst in series and generates H by oxygen reduction 2 O 2 The reaction is coupled with the epoxidation reaction of propylene, and the oxygen reduction generates H 2 O 2 The electrocatalytic catalyst and the propylene epoxidation thermal catalyst are cooperated as a cathode side catalyst to realize the in-situ preparation of propylene oxide by electrocatalytic oxygen reduction, and the method is compared with the traditional H 2 O 2 Compared with the production process for producing propylene oxide by a direct oxidation method, the invention has the advantages of mild reaction conditions, easy control of reaction, low energy consumption and avoidance of H 2 O 2 The problems of 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 yield up to 9mmol g prepared by electrocatalytic oxygen reduction in situ method in H-type electrolytic cell cat -1 h -1 (wherein each gram of catalyst refers to each gram of carbon-based electrocatalyst). The direct tandem connection of TS-1 with the electrocatalyst can shorten H compared to TS-1 dispersed in the electrolyte 2 O 2 The diffusion distance to the TS-1 surface is increased, so that the reaction rate is increased, and the TS-1 utilization rate and the propylene oxide yield are improved.
Drawings
FIG. 1 is a nitrogen adsorption-desorption isothermal graph of Co-O-C, and an embedded graph is a pore size distribution graph;
FIG. 2 is a wide angle XRD pattern for Co-O-C;
FIG. 3 is a LSV graph of Co-O-C and comparative O-C;
FIG. 4 is a diagram showing H of Co-O-C and comparative O-C 2 O 2 A selectivity map;
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 Yield map;
FIG. 7 is a graph showing propylene oxide yields for Co-O-C in different tandem schemes with TS-1;
FIG. 8 is a chromatogram of the product after optimal conditions of reaction;
FIG. 9 is a graph of analysis of chromatographic products of TS-1 dispersion into an electrode solution;
FIG. 10 is a schematic view of a flow cell cathode;
FIG. 11 is a graph of chromatographic analysis of electrolyte in a flow cell.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and the specific embodiments, for the purpose of illustrating the technical contents, the achieved objects and the effects of the present invention in detail.
Example 1
The preparation method of the transition metal cobalt monoatomic doped carbon-based electrocatalyst comprises the following specific steps:
(1) At room temperature, weighing 0.8172g of cobalt chloride hexahydrate in 2ml of deionized water, dissolving by ultrasonic, dispersing 500 μl of the solution into 0.5g of SBA-15 solid powder by an isovolumetric impregnation method, rapidly stirring and extruding to obtain light pink powder, transferring into a 50 ℃ oven for overnight drying to dry water, then performing hydrogen reduction, and obtaining the light pink powder, and adding hydrogen into H 2 Calcining for 2H at 450 ℃ in Ar mixed atmosphere, wherein the heating rate is 2 ℃/min, H 2 The flow rate of Ar was 74.9ml/min, and the brick-red solid powder was obtained after calcination and was designated as Co/SBA-15.
(2) Taking Co/SBA-15 in the step (1) as a template, taking 900 mu l of a carbon source solution (4 ml of furfuryl alcohol, 4ml of trimethylbenzene, 90.5mg of oxalic acid and ultrasonic dissolution of oxalic acid), soaking the carbon source solution in the 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 that the drying is carried out in the oven at 50 ℃ for 12h, the drying is carried out in the oven at 90 ℃ for 12h, the drying is carried out in the oven at 80 ℃ for 12h, and then placing the mixture into a tubular furnace for heating to 850 ℃ for calcination at a heating rate of 5 ℃/min under Ar atmosphere.
(3) Calcined samples were first prepared with 1.8M NaOH in water and alcohol (V Ethanol ：V Water and its preparation method =1:3) was soaked at 50 ℃ for 24h to remove template SBA-15. And (3) soaking the sample after the template is removed for 24 hours at the temperature of 50 ℃ by using 4M hydrochloric acid to remove metal cobalt nano particles, then carrying out 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 plot of a carbon-based electrocatalyst Co-O-C; as can be seen from the nitrogen absorption drawing, the catalyst Co-O-C is of a mesoporous structure, and the pore size distribution is concentrated at 3.0nm.
FIG. 2 is a wide angle XRD pattern for Co-O-C; as can be seen from the 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, so that the metal cobalt is distributed in an atomic form in the Co-O-C.
Comparative example 1 (not according to the invention)
The preparation of the comparative pure carbon material was carried out in accordance with step (2) of example 1, with the difference that the preparation was carried out only by directly using SBA-15 as a carbon source template, which was designated as O-C.
Example 2
Application of the carbon-based electrocatalyst Co-O-C of example 1 and the O-C of comparative example 1 to electrocatalytic oxygen reduction to H 2 O 2 The performance test comprises the following specific steps:
ORR activity and selectivity tests a four electrode system was established using a Rotating Ring Disk Electrode (RRDE), RRDE (glassy carbon disk + Pt ring) as the working electrode, a saturated Ag/AgCl reference electrode, and a platinum wire counter electrode. 6.2mg of Co-O-C and 6.2mg of O-C are respectively weighed, dispersed in 1ml of mixed solution consisting of 5wt.% of 50ul of Nafion, 665ul of deionized water and 285ul of ethanol by ultrasonic, 6 ul of electrocatalyst slurry is removed by a pipette and is dripped on the surface of a glass carbon disk of a ring disk electrode, and the mixture is naturally dried at room temperature to prepare a working electrode for oxygen reduction activity and selectivity test, wherein the catalyst loading is 0.3mg cm -2 。
H 2 O 2 Yield test using an H-cell to coat ordered cathode mesoporous carbon catalystThe carbon paper of (2) is used as a cathode, a platinum sheet is used as an anode, and a saturated Ag/AgCl is used as a reference electrode to assemble a three-electrode system. Dripping 80 μl of the catalyst slurry on two sides of carbon paper, with catalyst loading of 0.50mg cm -2 . Continuously introducing oxygen into the cathode side at a flow rate of 40ml min -1 . Electrolysis is carried out by adopting a potentiostatic method, and each potential is continuously electrolyzed for 7200s; cerium sulfate is used as a calibrating agent, and ultraviolet spectrum is combined to H in cathode liquid 2 O 2 And quantifying the content.
FIG. 3 is a LSV graph of Co-O-C and 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 Co-O-C, and the Co-O-C ring current is higher than O-C.
FIG. 4 is a diagram showing H of Co-O-C and comparative O-C 2 O 2 A selectivity map; from H 2 O 2 The selectivity of the catalyst Co-O-C is higher than that of H of O-C, co-O-C in the range of the test potential 2 O 2 The highest selectivity can reach 93 percent.
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 is close to 100% over a wide potential range.
FIG. 6 is H of Co-O-C 2 O 2 Yield map; as can be seen from FIG. 8, H of the catalyst Co-O-C 2 O 2 The yield increases 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 TS-1 catalyst are connected in series and applied to the in-situ preparation of propylene oxide by oxygen reduction, and the specific steps are as follows:
the series propylene epoxidation test adopts an H-type electrolytic cell, takes carbon paper coated with a carbon-based electrocatalyst and a TS-1 catalyst as a cathode, takes a platinum sheet as an anode, and takes saturated Ag/AgCl as a reference electrode to assemble a three-electrode system. A certain volume of TS-1 hot catalyst slurry and Co-O-C electrocatalyst slurry are dripped on two sides of carbon paper, and a mixed gas of oxygen and propylene is continuously introduced into the cathode side, wherein the flow rates are respectively 15ml min -1 . Carrying out electrolysis by adopting a potentiostatic method, and continuously electrolyzing each potential for 3 hours; cerium sulfate is adoptedAs a calibration agent, combining ultraviolet spectrum to H in the catholyte 2 O 2 The content was quantified, and the propylene oxide content in the catholyte was quantified by gas chromatography.
The mass of the carbon-based electrocatalyst and TS-1 thermal catalyst on the electrode plates manufactured in different series connection modes are respectively as follows:
the carbon-based catalyst and the TS-1 thermal catalyst are respectively coated on two sides of the carbon paper: 0.45mg of carbon-based catalyst and 0.9mg of TS-1 thermal catalyst;
carbon-based electrocatalyst covers TS-1 thermal catalyst on both sides of carbon paper: 1.2mg of carbon-based catalyst and 2.4mg of TS-1 thermal catalyst;
the carbon-based catalyst and 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 the different series connection modes is 1 x 1cm 2 。
FIG. 7 shows the comparison of epoxy yields under different conditions in the search, and FIG. 7 shows that the yields are highest when two catalysts are respectively dripped on two sides of the carbon paper.
FIG. 8 is a chromatogram of the product after optimal conditions of reaction; as can be seen from FIG. 8, the propylene oxide yield of the tandem catalyst is up to 9mmol g cat -1 h -1 。
Comparative example 2 (not according to the invention)
The method for preparing hydrogen peroxide by carbon-based catalyst Co-O-C oxygen reduction and preparing propylene oxide by TS-1 catalyst epoxidation propylene dispersed in electrolyte comprises the following specific steps:
the series propylene epoxidation test adopts an H-type electrolytic cell, takes carbon-based electro-catalysis as a cathode, 0.45mg of carbon-based catalyst and 1 x 1cm of working area 2 A three-electrode system is assembled by taking a platinum sheet as an anode and taking saturated Ag/AgCl as a reference electrode. Dispersing 0.9mg TS-1 in the cathode electrolyte, continuously introducing mixed gas of oxygen and propylene into the cathode side, and controlling the flow rate to 15ml min each -1 . Carrying out electrolysis by adopting a potentiostatic method, and continuously electrolyzing each potential for 3 hours; cerium sulfate is used as a calibrating agent, and ultraviolet spectrum is combined to H in cathode liquid 2 O 2 Quantitative determination of the content of propylene oxide in the catholyte by gas chromatographyThe amount was quantified.
No propylene oxide product was detected.
FIG. 9 is a graph of analysis of chromatographic products of TS-1 dispersion into an electrode solution.
Example 4
The method for preparing propylene oxide in situ by electrocatalytic oxygen reduction comprises the following specific steps:
the series propylene epoxidation test adopts a flowing electrolytic cell, a three-electrode system is assembled by taking 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 μl of the Co-O-C electrocatalyst slurry from example 2 was applied dropwise to carbon paper with a working area of 1 x 1cm 2 After drying, TS-1 hot catalyst slurry is dripped on the surface of 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, and the TS-1 hot catalyst loading is 2mg cm -2 Co-O-C electrocatalyst loading of 1mg cm -2 . Continuously introducing a mixed gas of oxygen and propylene into the cathode side, wherein the flow rate of the oxygen is 15ml min -1 Propylene flow rate of 15ml min -1 . Carrying out electrolysis by adopting a potentiostatic method, and continuously electrolyzing each potential for 3 hours; cerium sulfate is used as a calibrating agent, and ultraviolet spectrum is combined to H in cathode liquid 2 O 2 The content was quantified, and the propylene oxide content in the catholyte was quantified by gas chromatography.
FIG. 10 is a schematic view of a flow cell cathode; the TS-1 thermal catalyst is coated on the surface of the carbon-based electrocatalyst, and the coating area occupies half of the current collector.
FIG. 11 is a chromatographic chart of the electrolyte in a flow cell, as seen in FIG. 11, in situ hydrogen peroxide epoxidation with up to 11.68mmol g propylene oxide yield in the flow cell cat -1 h -1 。
Claims (9)
1. A method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series, which is characterized in that: the method comprises the steps of coating a TS-1 thermal catalyst and a 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 an electrode plate with a single-side covered catalyst; 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, coating the TS-1 thermal catalyst on the surface of the carbon-based electrocatalyst, wherein the area of the TS-1 thermal catalyst is smaller than that of the carbon-based electrocatalyst, or coating the TS-1 thermal catalyst on one side of the cathode current collector, and coating the carbon-based electrocatalyst on the surface of the TS-1 thermal catalyst.
2. A method for connecting a carbon-based electrocatalyst and a TS-1 thermal catalyst in series, which 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 coating the TS-1 thermal catalyst and the carbon-based electrocatalyst on two sides of the cathode current collector in sequence according to different sequences, or coating the carbon-based electrocatalyst and the TS-1 thermal catalyst on two sides of the cathode current collector respectively to obtain electrode plates with double-side covered catalysts; the TS-1 thermal catalyst and the carbon-based electrocatalyst are coated on two sides of a cathode current collector in sequence according to different sequences, wherein the method comprises the steps of firstly coating the carbon-based electrocatalyst on two sides of the cathode current collector, then coating the TS-1 thermal catalyst on the surface of the carbon-based electrocatalyst, wherein 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, or coating the TS-1 thermal catalyst on two sides of the cathode current collector, and then coating the carbon-based electrocatalyst on the surface of the TS-1 thermal catalyst.
3. A method of concatenating a carbon-based electrocatalyst with a TS-1 thermal catalyst according to claim 1 or 2, characterised in that: the mass ratio of the carbon-based electrocatalyst to the TS-1 thermal catalyst is 0.5:1-1:10.
4. A method of concatenating a carbon-based electrocatalyst with a TS-1 thermal catalyst according to claim 1 or 2, characterised in that: the cathode current collector is carbon paper, carbon cloth or carbon felt.
5. A method of concatenating a carbon-based electrocatalyst with a TS-1 thermal catalyst according to claim 1 or 2, characterised in that: the carbon-based electrocatalyst is a transition metal monoatomic doped carbon-based electrocatalyst.
6. A method of concatenating a carbon-based electrocatalyst with a TS-1 thermal catalyst according to claim 5, wherein: the preparation method of the transition metal monoatomic doped carbon-based electrocatalyst comprises the following steps:
s1, preparing transition metal M salt water solution, dispersing the solution into SBA-15 solid powder by an isovolumetric impregnation method, drying and then adding the solution into H 2 Carrying out hydrogen reduction in Ar atmosphere to obtain a sample of SBA-15 loaded transition metal particles, which is designated as M/SBA-15;
s2, taking M/SBA-15 as a template, taking a carbon source solution to dip the carbon source solution into the M/SBA-15 solid powder in an equal volume, carrying out aging polymerization, and placing the mixture in Ar atmosphere for calcination;
s3, performing alkali washing on the obtained black solid powder by using a sodium hydroxide aqueous solution to remove the SBA-15 template, performing acid washing by using a hydrochloric acid solution to remove transition metal particles, and finally obtaining the transition metal single-atom doped carbon-based electrocatalyst.
7. A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction is characterized in that: the method comprises the following steps:
s1, using the electrode plate with one side covered with the catalyst obtained by the serial connection method of claim 1 as a cathode to assemble a flow type electrolytic cell;
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 each potential.
8. A method for preparing propylene oxide in situ by electrocatalytic oxygen reduction is characterized in that: the method comprises the following steps:
s1, an H-type electrolytic cell is assembled by taking electrode plates with double sides covered with catalysts, which are obtained by the serial connection method of claim 2, 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 a constant potential mode, and continuously electrolyzing each potential.
9. A method for producing propylene oxide in situ by electrocatalytic oxygen reduction as set forth in claim 7 or 8, wherein: the carbon-based electrocatalyst in the electrode slice is contacted with the electrolyte.
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| 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 |
| CN112609199A (en) * | 2020-12-11 | 2021-04-06 | 南京信息工程大学 | Electrocatalysis H2O2Solution preparation method and device |
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| 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 |
| CN112609199A (en) * | 2020-12-11 | 2021-04-06 | 南京信息工程大学 | Electrocatalysis H2O2Solution preparation method and device |
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