CN112169792A - Flexible Ag-Pd/ZrO2Preparation method of @ carbon fiber cloth catalyst - Google Patents
Flexible Ag-Pd/ZrO2Preparation method of @ carbon fiber cloth catalyst Download PDFInfo
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- CN112169792A CN112169792A CN202011206994.4A CN202011206994A CN112169792A CN 112169792 A CN112169792 A CN 112169792A CN 202011206994 A CN202011206994 A CN 202011206994A CN 112169792 A CN112169792 A CN 112169792A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 52
- 239000004744 fabric Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000004917 carbon fiber Substances 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 8
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 abstract 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 239000013543 active substance Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/90—Selection of catalytic material
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses flexible Ag-Pd/ZrO2The preparation method of the @ carbon fiber cloth catalyst comprises the following specific steps: dissolving carbon fiber cloth in acetone solution, carrying out ultrasonic cleaning, then carrying out ultrasonic cleaning by using deionized water and alcohol in sequence, drying, and then arranging the carbon fiber on ZrOCl2·8H2O、PdCl2And AgCl2Adding ammonia water dropwise into the mixed solution until the pH value is 8-14, then placing the mixed solution into a reaction kettle for hydrothermal reaction, finally cleaning the reaction solution with deionized water, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst. The flexible Ag-Pd/ZrO prepared by the method2The catalyst components, the size and the crystallization degree of the nano particles of the @ carbon fiber cloth can be regulated, and the loaded nano particles and the flexible carrier have strong bonding force and high stability; effectively reduces the catalyst cost under the condition of keeping high catalytic performance. At the same time, it has excellent conductivity.
Description
Technical Field
The invention belongs to the technical field of preparation of catalytic materials, and particularly relates to flexible Ag-Pd/ZrO2A preparation method of a @ carbon fiber cloth catalyst.
Background
In recent years, flexible electronic products have attracted attention due to their portability, portability and foldability, so that flexible power supply equipment has been developed rapidly and is widely used in new energy fields such as supercapacitors, rechargeable batteries and solar cells.
Flexible fuel cells are essentially a class of flexible catalytic conversion devices, and flexible catalysts are an indispensable important material. The catalyst breaks through the limitation that the original supported catalyst is limited to hard and brittle carriers such as metal, oxide and the like. At present, the preparation method of the flexible catalyst mainly comprises the steps of dispersing and bonding active powder to load on a flexible substrate through a binder, or dipping the flexible substrate into mother liquor containing active ions to be sintered so that active substances grow on the flexible substrate in situ, or adding a material with catalytic activity into stock solution for preparing fibers to obtain the active fiber catalyst through electrostatic spinning, and the like. The method for dispersedly loading the active powder to the flexible substrate has simple preparation process and easy processing, but is easy to seriously agglomerate on the surface of the fabric under the action of a coupling agent or a binder, so that the catalytic activity of the fabric is reduced; when preparing a flexible catalyst by growing an active substance in situ on a flexible substrate by impregnation-sintering, the method is limited because most of the fiber fabrics are not resistant to high temperature; the active catalytic material is added into the stock solution of electrostatic spinning, and the flexible catalyst prepared by a protofilament improvement method has the characteristics of durability and the like, but the doped nano powder is easily embedded into the fiber, the catalytic performance of the catalyst cannot be fully exerted, the process is complex, the dosage of the reagent is large, and the problems of nano powder agglomeration, spinning broken ends and the like can occur in the blending spinning process.
Disclosure of Invention
The invention aims to provide flexible Ag-Pd/ZrO2The simple preparation method of the @ carbon fiber cloth catalyst effectively solves the problem of poor conductivity caused by bonding an active substance on a flexible substrate through a binder in the prior art.
The technical scheme adopted by the invention is that the flexible Ag-Pd/ZrO2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 8-14, and performing ultrasonic treatment at room temperature for a period of time to obtain a precursor;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst.
The present invention is also characterized in that,
in the step 1, the time of ultrasonic cleaning is 30 min.
In step 2, PdCl2And AgCl2In a molar ratio of 5-1: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 15: 5-1; pd loading is 0.1-3 wt%; ag loading is 0.1-3 wt%.
In the step 2, the ultrasonic treatment time is 1-3 h; the mass fraction of the ammonia water is 10-20%.
In step 3, the hydrothermal reaction conditions are as follows: heating the polytetrafluoroethylene high-pressure reaction kettle to 150 ℃ and 220 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 1-5 h.
In the step 3, the drying temperature is 50 ℃ and the drying time is 4 h.
The beneficial effect of the invention is that,
the flexible load type Ag-Pd/ZrO prepared by the method2The catalyst components, the size and the crystallization degree of the nano particles of the @ carbon fiber cloth can be regulated, and the loaded nano particles and the flexible carrier have strong bonding force and high stability; the preparation process is simple and easy to control, can be used for mass preparation, and effectively reduces the cost of the catalyst under the condition of keeping high catalytic performance. Meanwhile, the conductive material has excellent conductivity, can be freely cut, is easy to install in reactors of different shapes, has a large active reaction site area, is rapid in reaction kinetics, and is convenient to recover.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 8-14, and performing ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 5-1: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 15: 5-1; pd loading is 0.1-3 wt%;ag loading amount is 0.1-3 wt%; the ultrasonic treatment time is 1-3 h; the mass fraction of the ammonia water is 10-20%;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating the polytetrafluoroethylene high-pressure reaction kettle to 160-220 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 1-5 h; the drying temperature is 50 ℃ and the drying time is 4 h.
The invention adopts one-step hydrothermal technology to prepare the flexible load type Ag-Pd/ZrO for the fuel cell2The method has simple and easily-controlled preparation process, can be used for mass production, and can accurately regulate Pd, Ag and ZrO by changing liquid components and hydrothermal process parameters2The amount of supported, the degree of crystallization, and the particle size. In the preparation process, a coupling agent or a bonding agent which influences the catalytic performance and reduces the conductivity is not required to be added, and the subsequent high-temperature heat treatment is not required, so that the production cost is low.
Example 1
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 10, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 1: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 5: 1; pd loading was 1 wt%; ag loading of 1 wt%; ultrasonic treatmentThe processing time is 1 h; the mass fraction of ammonia water is 15 percent;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 190 ℃ at the speed of 2 ℃/min, and preserving heat for 3 hours; the drying temperature is 50 ℃ and the drying time is 4 h.
Example 2
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 11, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 1: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 10: 1; pd loading was 1.5 wt%; ag loading was 1.5 wt%; the ultrasonic treatment time is 3 h; the mass fraction of ammonia water is 15 percent;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 190 ℃ at the speed of 3 ℃/min, and preserving heat for 3 hours; the drying temperature is 50 ℃ and the drying time is 4 h.
Example 3
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 12, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 2: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 3: 1; pd loading was 2 wt%; ag loading of 1 wt%; the ultrasonic treatment time is 3 h; the mass fraction of the ammonia water is 20 percent;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 200 ℃ at the speed of 2-5 ℃/min, and preserving heat for 2 h; the drying temperature is 50 ℃ and the drying time is 4 h.
Example 4
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 13, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 3: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 5: 1; pd loading was 3 wt%; ag loading of 1 wt%; the ultrasonic treatment time is 1 h; the mass fraction of the ammonia water is 20 percent;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 180 ℃ at the speed of 2-5 ℃/min, and preserving heat for 4 h; the drying temperature is 50 ℃ and the drying time is 4 h.
Example 5
The flexible Ag-Pd/ZrO of the invention2The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
wherein the time of ultrasonic cleaning is 30min each time;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 12, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
wherein PdCl is2And AgCl2In a molar ratio of 15: 3; PdCl2And ZrOCl2·8H2The molar ratio of O is 15: 1; pd loading was 2 wt%; ag loading of 0.5 wt%; the ultrasonic treatment time is 3 h; the mass fraction of the ammonia water is 20 percent;
step 3, putting the precursor into a polymerCarrying out hydrothermal reaction in a tetrafluoroethylene high-pressure reaction kettle, after the reaction is finished, cleaning the reaction solution with deionized water, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 200 ℃ at the speed of 2-5 ℃/min, and preserving heat for 5 hours; the drying temperature is 50 ℃ and the drying time is 4 h.
For the flexible Ag-Pd/ZrO prepared in examples 1-52The @ carbon fiber cloth catalyst is placed in alkali liquor to carry out electrocatalytic oxidation on methanol, and the catalytic activity data of the catalyst is shown in table 1.
TABLE 1 catalytic Activity of samples 1-5 for the electrocatalytic oxidation of methanol in alkaline solution
The invention relates to flexible Ag-Pd/ZrO2The simple preparation method of the @ carbon fiber cloth catalyst effectively solves the problem of poor conductivity caused by bonding an active substance on a flexible substrate through a binder in the prior art, and does not need any subsequent heat treatment. The prepared catalyst simultaneously uses Ag, Pd and ZrO2The nano particles are loaded on the carbon fiber cloth carrier with good conductivity and high flexibility, the catalytic performance is not affected by folding, the conductivity is good, no additional conductive substance is needed, the carbon fiber cloth carrier can be installed in reactors with different shapes after being cut, and the carbon fiber cloth carrier has the advantages of large active reaction site area, fast reaction kinetics, easy recovery and the like, and can effectively reduce the catalyst cost under the condition of keeping high catalytic performance.
Claims (6)
1. Flexible Ag-Pd/ZrO2The preparation method of the @ carbon fiber cloth catalyst is characterized by comprising the following steps of:
dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning to remove surface oil stains, then ultrasonically cleaning with deionized water and alcohol in sequence, and naturally drying for later use;
step 2, arranging the carbon fiber obtained in the step 1 on ZrOCl containing a certain molar ratio2·8H2O、PdCl2And AgCl2Adding ammonia water into the mixed solution dropwise until the pH value of the mixed solution is 8-14, and performing ultrasonic treatment at room temperature for a period of time to obtain a precursor;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, washing the reaction solution with deionized water after the reaction is finished, and drying to obtain the flexible Ag-Pd/ZrO2@ carbon fiber cloth catalyst.
2. Flexible Ag-Pd/ZrO according to claim 12The preparation method of the @ carbon fiber cloth catalyst is characterized in that in the step 1, the time of ultrasonic cleaning is 30min each time.
3. Flexible Ag-Pd/ZrO according to claim 12The preparation method of the @ carbon fiber cloth catalyst is characterized in that in the step 2, PdCl2And AgCl2In a molar ratio of 5-1: 1; PdCl2And ZrOCl2·8H2The molar ratio of O is 15: 5-1; pd loading is 0.1-3 wt%; ag loading is 0.1-3 wt%.
4. Flexible Ag-Pd/ZrO according to claim 12The preparation method of the @ carbon fiber cloth catalyst is characterized in that in the step 2, the ultrasonic treatment time is 1-3 h; the mass fraction of the ammonia water is 10-20%.
5. Flexible Ag-Pd/ZrO according to claim 12The preparation method of the @ carbon fiber cloth catalyst is characterized in that in the step 3, the hydrothermal reaction conditions are as follows: heating the polytetrafluoroethylene high-pressure reaction kettle to 160-220 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 1-5 h.
6. Flexible Ag-Pd/ZrO according to claim 12The preparation method of the @ carbon fiber cloth catalyst is characterized in that in the step 3, the drying temperature is 50 ℃ and the drying time is 4 hours.
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