CN112169792B - Flexible Ag-Pd/ZrO 2 Preparation method of @ carbon fiber cloth catalyst - Google Patents

Flexible Ag-Pd/ZrO 2 Preparation method of @ carbon fiber cloth catalyst Download PDF

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CN112169792B
CN112169792B CN202011206994.4A CN202011206994A CN112169792B CN 112169792 B CN112169792 B CN 112169792B CN 202011206994 A CN202011206994 A CN 202011206994A CN 112169792 B CN112169792 B CN 112169792B
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宋衍滟
陈莹
张中华
丁浪
陈玺
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Shenzhen Wanzhida Technology Co ltd
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Abstract

The invention discloses flexible Ag-Pd/ZrO 2 The 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 ZrOCl 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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/ZrO 2 @ carbon fiber cloth catalyst. The flexible Ag-Pd/ZrO prepared by the method 2 The 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

Flexible Ag-Pd/ZrO 2 Preparation method of @ carbon fiber cloth catalyst
Technical Field
The invention belongs to the technical field of preparation of catalytic materials, and particularly relates to a catalystAnd a flexible Ag-Pd/ZrO 2 A 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/ZrO 2 The simple preparation method of the @ carbon fiber cloth catalyst effectively solves the problem of poor conductivity caused by the fact that an active substance is bonded on a flexible substrate through a binder in the prior art.
Produced by the inventionThe technical proposal is that the flexible Ag-Pd/ZrO 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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/ZrO 2 @ carbon fiber cloth catalyst.
The present invention is also characterized in that,
in the step 1, the time of ultrasonic cleaning is 30min.
In step 2, pdCl 2 And AgCl 2 In a molar ratio of 5-1:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 15:5-1; pd loading is 0.1-3wt%; ag loading is 0.1-3wt%.
In the step 2, the ultrasonic treatment time is 1-3h; 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 150-220 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 1-5h.
In the step 3, the drying temperature is 50 ℃ and the drying time is 4h.
The beneficial effect of the invention is that,
the flexible load type Ag-Pd/ZrO prepared by the method 2 The 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 large-scale preparation, and has high catalytic performanceEffectively reduces the cost of the catalyst. 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 invention 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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 2 And AgCl 2 In a molar ratio of 5-1:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 15:5-1; pd loading is 0.1-3wt%; ag loading amount is 0.1-3wt%; the ultrasonic treatment time is 1-3h; 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/ZrO 2 @ carbon fiber cloth catalyst;
the hydrothermal reaction conditions are as follows: heating a polytetrafluoroethylene high-pressure reaction kettle to 160-220 ℃ at the speed of 2-5 ℃/min, and preserving heat for 1-5h; the drying temperature is 50 ℃ and the drying time is 4h.
The invention adopts one-step hydrothermal technology to prepare the flexible load type Ag-Pd/ZrO for the fuel cell 2 The method has simple and easily-controlled preparation process and can be used for mass production of the @ carbon fiber clothProduction, and Pd, ag and ZrO can be accurately regulated and controlled by changing liquid components and hydrothermal process parameters 2 The 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 invention 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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 is 2 And AgCl 2 In a molar ratio of 1:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 5:1; pd loading was 1wt%; ag loading of 1wt%; the ultrasonic treatment time is 1h; 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/ZrO 2 @ 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 4h.
Example 2
The flexible Ag-Pd/ZrO of the invention 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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 is 2 And AgCl 2 In a molar ratio of 1:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 10:1; pd loading was 1.5wt%; ag loading was 1.5wt%; the ultrasonic treatment time is 3h; 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/ZrO 2 @ 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 4h.
Example 3
The flexible Ag-Pd/ZrO of the invention 2 The preparation method of the @ carbon fiber cloth catalyst is specifically implemented according to the following steps:
step 1, dissolving carbon fiber cloth in an acetone solution, ultrasonically cleaning, removing oil stains on the surface, then sequentially ultrasonically cleaning with deionized water and alcohol, 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding ammonia water to the mixed solution dropwise until the pH value of the mixed solution is 12, and performing ultrasonic treatment at room temperature for a period of time to obtain the precursorDriving a body;
wherein PdCl is 2 And AgCl 2 In a molar ratio of 2:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 3:1; pd loading was 2wt%; ag loading of 1wt%; the ultrasonic treatment time is 3h; 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/ZrO 2 @ 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 2h; the drying temperature is 50 ℃ and the drying time is 4h.
Example 4
The flexible Ag-Pd/ZrO of the invention 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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 is 2 And AgCl 2 In a molar ratio of 3:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 5:1; pd loading was 3wt%; the Ag loading amount is 1wt%; the ultrasonic treatment time is 1h; 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/ZrO 2 @ 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 4h; the drying temperature is 50 ℃, and the drying time is 4h.
Example 5
The flexible Ag-Pd/ZrO of the invention 2 The 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 ratio 2 ·8H 2 O、PdCl 2 And AgCl 2 Adding 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 is 2 And AgCl 2 In a molar ratio of 15:3; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 15:1; pd loading was 2wt%; ag loading of 0.5wt%; the ultrasonic treatment time is 3h; the mass fraction of the ammonia water is 20 percent;
step 3, placing the precursor in a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal reaction, after the reaction is finished, cleaning the reaction solution with deionized water, and drying to obtain the flexible Ag-Pd/ZrO 2 @ 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 4h.
For the flexible Ag-Pd/ZrO prepared in examples 1-5 2 The @ 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
Figure BDA0002757388000000081
Figure BDA0002757388000000091
The invention relates to flexible Ag-Pd/ZrO 2 The 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 ZrO 2 The 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 (3)

1. Flexible Ag-Pd/ZrO 2 The 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 ratio 2 ·8H 2 O、PdCl 2 Adding ammonia water into the mixed solution of AgCl, then dropwise adding ammonia water into the mixed solution until the pH value of the mixed solution is 8-14, and carrying out ultrasonic treatment at room temperature for a period of time to obtain a precursor;
PdCl 2 and AgCl in a molar ratio of 5-1:1; pdCl 2 And ZrOCl 2 ·8H 2 The molar ratio of O is 15:5-1; pd loading amount is 0.1-3wt%; ag loading amount is 0.1-3wt%;
the ultrasonic treatment time is 1-3h; 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/ZrO 2 @ 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 1-5h.
2. Flexible Ag-Pd/ZrO according to claim 1 2 The 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 1 2 The 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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