CN114551907A - Carbon fiber loaded nickel-manganese oxide composite material and preparation method and application thereof - Google Patents
Carbon fiber loaded nickel-manganese oxide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon fiber loaded nickel-manganese oxide composite material, a preparation method and application thereof, wherein the composite material is prepared by the following steps: (a) preparing a carbon fiber precursor by an electrostatic spinning method; (b) preparing a mixed solution of a nickel source and a manganese source, adding polyvinylpyrrolidone into the mixed solution, then adding the carbon fiber precursor, and performing hydrothermal treatment for 2-10h in a reaction kettle at the temperature of 100-; (c) washing and drying the product obtained in the step (b), and then carrying out oxidation treatment at the oxidation temperature of 500-650 ℃ for 3-6 h. The nickel manganese oxide is uniformly dispersed on the carbon fiber material, the synergistic effect among the materials is fully utilized, the electrochemical performance of the material is further improved, and the obtained material has good catalytic performance and is suitable for large-scale application.
Description
Technical Field
The invention relates to the technical field of nano composite material preparation, in particular to a carbon fiber loaded nickel-manganese oxide composite material and a preparation method and application thereof.
Background
Zinc airThe battery has the characteristics of high specific energy density, safety, stability, environmental friendliness and the like, and is one of typical representatives of a new generation of electrochemical energy storage devices. Zinc air cell air electrode materials have been the focus of recent research, transition metal based catalysts, such as MnO2、Co3O4、NiCo2O4The preparation cost is low, but the transition metal base catalyst material has poor conductivity, especially some transition metal oxides; the carbon nano material catalyst has high specific surface area and high conductivity, and can be used as a conductive agent or a catalyst carrier in an air electrode. Therefore, how to combine the transition metal-based catalyst material and the carbon nanomaterial catalyst organically, i.e. the metal oxide and the carbon material, to obtain a material with high catalytic activity has been the focus of attention of researchers.
Carbon fiber is a carbon material with regular appearance, many holes and large specific surface area, and is widely popular with researchers. Wang adds ZIFs into a PAN system for electrospinning, and finally obtains the hierarchical porous fiber with excellent catalytic ORR performance. The carbon fiber prepared by the method has the following technical problems: when the ZIFs are directly used for electrospinning, the ZIFs inside the fiber are difficult to contact with the surface for reaction, and the characteristic of high active site density of the ZIFs is not favorably utilized to the maximum extent.
Zhang utilizes a simple one-step hydrothermal method to uniformly stir a precursor nickel nitrate solution, a manganese acetate solution, a hexamethylenetetramine dispersant and the like, and NiO/Ni is obtained through hydrothermal treatment6MnO8And (c) a complex. The simple material is mainly in a flower-shaped and loose structural shape on the outside. The catalyst material prepared by the method has the defect of poor conductivity, so that the material has low catalytic activity and cannot be used for an air electrode of a zinc-air battery.
In the method for preparing the carbon fiber and metal oxide composite material, the electrostatic spinning technology has the characteristics of small material diameter, controllable morphology, simple preparation method and universality, but for the catalyst, the components and the structure are important factors influencing the catalytic efficiency. Relying solely on electrospinning techniques, the components of the catalyst cannot be rationally designed and the catalytic interface cannot be constructed to maximize the utilization of the active species in the material.
Therefore, the metal oxide is loaded on the carbon nanofibers by using the technology of combining electrostatic spinning and hydrothermal reaction through low-cost and commercialized raw materials, and the excellent electrode material obtained has obvious economic value.
Disclosure of Invention
The invention aims to provide a carbon fiber loaded nickel-manganese oxide composite material, and a preparation method and application thereof, so as to solve the problems of high cost, low catalytic activity and non-ideal battery performance of the existing material.
The technical scheme of the invention is as follows: a carbon fiber-loaded nickel-manganese oxide composite material is prepared by the following method:
(a) preparing a carbon fiber precursor by an electrostatic spinning method;
(b) preparing a mixed solution of a nickel source and a manganese source, adding polyvinylpyrrolidone into the mixed solution, then adding the carbon fiber precursor, and performing hydrothermal treatment for 2-10h in a reaction kettle at the temperature of 100-;
(c) washing and drying the product obtained in the step (b), and then carrying out oxidation treatment at the oxidation temperature of 500-650 ℃ for 3-6 h. The carbon element in the composite material exists in a carbon fiber structure, and the diameter of the carbon element is 1-1.5 microns.
In the step (a), polyacrylonitrile and N, N-dimethylformamide are mixed and stirred for 10-14h at the temperature of 70-80 ℃ to prepare a spinning solution, then electrostatic spinning is carried out on the spinning solution under the conditions that the voltage is 15-20kV, the distance between a spray head and a roller is 20-30cm, and the temperature is 20-25 ℃, then drying is carried out for 20-24h at the temperature of 50-60 ℃, finally the dried spinning is put into a tubular furnace under the air atmosphere, the temperature is raised to 270-900 ℃ at the rate of 1-3 ℃/min, the temperature is kept for 1-2h for pre-oxidation, then under the nitrogen atmosphere, the temperature is raised to 800-900 ℃ at the rate of 3-5 ℃/min, and the temperature is kept for 1-2h for calcination, thus obtaining the carbon fiber precursor.
In the step (b), the concentration of nickel metal ions in the mixed solution is 0.1-0.5mol/L, the concentration of manganese metal ions is 0.017-0.083mol/L, and the ratio of the concentration of nickel metal ions to the concentration of manganese metal ions is controlled to be 100: 10-20.
In the step (b), the nickel source comprises nickel nitrate, the manganese source comprises manganese acetate, and the solvent of the mixed solution is methanol.
In the step (b), the ratio of polyvinylpyrrolidone, carbon fiber precursor and mixed solution is 0.4-0.6 g: 0.2-0.4 g: 10 mL.
In the step (c), the washing agent used for washing is water, and the drying conditions are as follows: drying at 60-100 deg.C for 12-24 hr.
A preparation method of a carbon fiber loaded nickel-manganese oxide composite material comprises the following steps:
(a) preparing a carbon fiber precursor by an electrostatic spinning method;
(b) preparing a mixed solution of a nickel source and a manganese source, and controlling the ratio of the concentration of nickel metal ions to the concentration of manganese metal ions to be 100: 10-20, wherein the concentration of nickel metal ions in the mixed solution is 0.1-0.5mol/L, and the concentration of manganese metal ions is 0.017-0.083 mol/L; adding polyvinylpyrrolidone into the mixed solution, then adding the carbon fiber precursor, and performing hydrothermal treatment for 2-10h in a reaction kettle at the temperature of 100-;
(c) washing and drying the product obtained in the step (b), and then carrying out oxidation treatment at the oxidation temperature of 500-650 ℃ for 3-6 h.
In the step (a), polyacrylonitrile and N, N-dimethylformamide are mixed and stirred for 10-14h at the temperature of 70-80 ℃ to prepare a spinning solution, then electrostatic spinning is carried out on the spinning solution under the conditions that the voltage is 15-20kV, the distance between a spray head and a roller is 20-30cm, and the temperature is 20-25 ℃, then drying is carried out for 20-24h at the temperature of 50-60 ℃, finally the dried spinning is put into a tubular furnace under the air atmosphere, the temperature is raised to 270-900 ℃ at the rate of 1-3 ℃/min, the temperature is kept for 1-2h for pre-oxidation, then under the nitrogen atmosphere, the temperature is raised to 800-900 ℃ at the rate of 3-5 ℃/min, and the temperature is kept for 1-2h for calcination, thus obtaining the carbon fiber precursor.
In the step (b), the nickel source comprises nickel nitrate, the manganese source comprises manganese acetate, and the solvent of the mixed solution is methanol; the proportion of polyvinylpyrrolidone, carbon fiber precursor and mixed solution is 0.4-0.6 g: 0.2-0.4 g: 10 mL. In the step (c), the washing agent used for washing is water, and the drying conditions are as follows: drying at 60-100 deg.C for 12-24 hr.
The use of the above composite material in an air battery.
Compared with the prior art, the carbon fiber loaded nickel-manganese oxide composite material has the following advantages:
1. the invention adopts the mixed solution of PAN/DMF as the spinning solution, and compared with other electrostatic spinning polymer materials, Polyacrylonitrile (PAN) has the advantages of excellent performance, good compatibility, very low toxicity, mild condition, greenness and environmental protection;
2. the nickel manganese oxide is uniformly dispersed on the carbon fiber material, the synergistic effect among the materials is fully utilized, the electrochemical performance of the material is further improved, and the obtained material has good catalytic performance;
3. the invention adopts the technology of combining electrostatic spinning with a hydrothermal method, the technology has the advantages of easy operation and low cost in the process of preparing the carbon fiber loaded metal oxide material, the preparation method and the process are simple, the product performance is stable, the preparation method is suitable for large-batch preparation, and the post-treatment process is simple.
Drawings
FIG. 1 is a scanning electron microscope image of the carbon fiber loaded Ni Mn LDH prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the carbon fiber-supported nickel manganese oxide composite material prepared in example 1 of the present invention.
Fig. 3 is an XRD spectrum of the carbon fiber-supported nickel manganese oxide composite material prepared in example 1 of the present invention.
Fig. 4 is a scanning electron microscope image of the carbon fiber-loaded nickel manganese oxide composite material precursor prepared in comparative example 1 of the present invention.
FIG. 5 is a scanning electron microscope image of the carbon fiber-supported nickel manganese oxide composite material prepared in comparative example 1 of the present invention.
Fig. 6 is an XRD spectrum of the carbon fiber-supported nickel manganese oxide composite material prepared in comparative example 1 of the present invention.
FIG. 7 is an LSV curve of ORR obtained by testing carbon fiber-supported nickel manganese oxide composites prepared in example 1 and comparative example 1 of the present invention in a 0.1mol/L KOH solution.
FIG. 8 is an LSV curve of OER measured in 0.1mol/L KOH solution for carbon fiber-supported nickel manganese oxide composites prepared in example 1 and comparative example 1 of the present invention.
Fig. 9 is a charge-discharge curve of the carbon fiber-loaded nickel-manganese oxide composite material prepared in example 1 of the present invention applied to a zinc-air battery.
Fig. 10 is a power density curve of the carbon fiber-supported nickel-manganese oxide composite material prepared in example 1 of the present invention applied to a zinc-air battery.
Fig. 11 is a cycle curve of the carbon fiber-supported nickel manganese oxide composite material prepared in example 1 of the present invention applied to a zinc-air battery.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
Example 1
The preparation method of the carbon fiber loaded nickel-manganese oxide composite material comprises the following steps:
step 1) preparing a precursor by an electrostatic spinning method, mixing 1g of Polyacrylonitrile (PAN) and 9g N, N-Dimethylformamide (DMF) at 75 ℃, stirring for 12h vigorously to dissolve completely to obtain a spinning solution for electrostatic spinning, spinning the spinning solution under the conditions that the voltage is 18kv, the distance between a spray head and a roller is 25cm, and the temperature is 25 ℃, and drying for 24h in a 60 ℃ oven.
And finally, putting the dried spinning into a tubular furnace in an air atmosphere, heating to 280 ℃ at a heating rate of 2 ℃/min, preserving heat for 1.5h for pre-oxidation, heating to 850 ℃ at a heating rate of 4 ℃/min in a nitrogen atmosphere, preserving heat for 1.5h for calcination, and thus obtaining the pure carbon fiber precursor.
Step 2) preparing the carbon fiber loaded nickel-manganese oxide composite material by a hydrothermal combined oxidation method, and dissolving nickel nitrate and manganese acetate in 10mL of methanol solution, wherein the molar concentration of nickel ions is 0.1mol/L, and the molar concentration of manganese ions is 0.017 mol/L. And adding 0.5g of PVP into the 10ml of methanol solution, then putting 0.32g of the treated carbon fiber precursor and the methanol mixed solution into an autoclave, placing the autoclave at the temperature of 150 ℃ for hydrothermal treatment for 4h, cooling, carrying out solid-liquid separation, washing with water, and drying at 60 ℃ for 24h to obtain the carbon fiber loaded Ni Mn LDH. And oxidizing for 4 hours at 600 ℃ in the air atmosphere to obtain the carbon fiber supported nickel-manganese oxide catalyst.
The microscopic morphologies of the carbon fiber-loaded Ni Mn LDH and carbon fiber-loaded nickel manganese oxide composite material obtained by scanning electron microscope testing are shown in FIGS. 1 and 2. From the figure, it can be seen that the Ni Mn LDH is uniformly loaded on the carbon fiber, and the nanosheet obtained through the oxidation process is porous and is also uniformly loaded on the carbon fiber.
The composition of the carbon fiber-supported nickel manganese oxide composite material is shown in fig. 3.
The electrochemical performance test method of the carbon fiber loaded nickel-manganese oxide composite material comprises the following steps: linear voltammetric scans (LSVs) were obtained at room temperature under a three-electrode system from CHI 760E electrochemical workstation (CH Instrument, Inc.) in conjunction with a rotating disk electrode testing apparatus. Wherein, the Pt wire electrode and the Ag/AgCl (3M) electrode are respectively used as a counter electrode and a reference electrode. A Rotating Disk Electrode (RDE) was used as the working electrode and 0.1M KOH as the electrolyte. The catalyst ink was prepared as follows: 5mg of catalyst and 0.02mL of 5 wt% Nafion solution were dispersed in 1mL of ethanol and sonicated for 10min to form a uniform catalyst ink. For the LSV test, 0.01mL of catalyst ink was dropped onto the rotating disk electrode.
As shown in fig. 7 and 8, the following results were obtained: the half-wave potential of the carbon fiber loaded nickel-manganese oxide composite catalyst for catalyzing the oxygen reduction reaction is about 0.81V, and the limiting current density is 5.07mA/cm 2. As shown in FIG. 8, the carbon fiber supported nickel manganese oxide can provide 10mA/cm in 0.1mol/L KOH solution at a voltage of 1.585V2The current density of (1). Therefore, the carbon fiber loaded nickel-manganese oxide composite material prepared by the method has high-efficiency ORR and OER catalytic performance.
Comparative example 1
The carbon fiber-loaded nickel-manganese oxide is prepared by adopting a method of direct electrostatic spinning after mixing, and the experimental raw materials and reagents which are not particularly described in the specific steps are the same as those of the carbon fiber-loaded nickel-manganese oxide composite material in the embodiment 1.
The difference lies in that: the comparative example adopts a method of directly electrostatic spinning after mixing to prepare the carbon fiber loaded nickel manganese oxide.
And (3) preparing carbon fiber loaded nickel-manganese oxide by direct electrostatic spinning after mixing:
step 1) preparing a precursor by an electrostatic spinning method, mixing 2g of polyvinylpyrrolidone (PVP) and 11.34g N, N-Dimethylformamide (DMF) at 70 ℃, stirring for 1h vigorously until the two are completely dissolved, adding 2mmol of nickel nitrate and 1mmol of manganese acetate into the mixture at room temperature, stirring for 12h to obtain a spinning stock solution for electrostatic spinning, starting spinning the spinning stock solution under the conditions that the voltage is 21kV and the distance between a nozzle and a roller is 10cm, and finally drying for 24h in an oven at 60 ℃ to obtain the precursor;
and 2) calcining at high temperature to prepare the carbon fiber loaded nickel-manganese oxide composite material, putting the product obtained in the step 1) into a muffle furnace, calcining at 550 ℃ in the air atmosphere, heating at the rate of 5 ℃/min, and preserving heat for 3 hours to obtain the carbon fiber loaded nickel-manganese oxide composite material.
The micro-morphology of the electrospun precursor prepared in the comparative example is shown in fig. 4 by scanning electron microscope test, and the micro-morphology of the carbon fiber loaded nickel-manganese oxide composite material is shown in fig. 5 by scanning electron microscope test.
The composition of the carbon fiber-supported nickel manganese oxide composite material prepared by the comparative example is shown in fig. 6.
The carbon fiber-loaded nickel-manganese oxide composite material prepared by the direct electrostatic spinning method after mixing is subjected to electrochemical test, the test method is the same as that of the example 1, and the carbon fiber-loaded nickel-manganese oxide composite material prepared by the direct electrostatic spinning method has no lower platform during the catalytic oxygen reduction reaction, as shown in fig. 7, which indicates that four-electron transfer does not occur. As shown in FIG. 8, the carbon fiber supported nickel manganese oxide can provide 10mA cm in 0.1mol/L KOH solution at a voltage of 1.882V-2The current density of the zinc-air battery is low, so that the electrocatalyst prepared by the method is not beneficial to the improvement of the performance of the zinc-air battery.
Example 2
The preparation method of the carbon fiber loaded nickel-manganese oxide composite material comprises the following steps:
step 1) is the same as in example 1.
Step 2) preparing the carbon fiber loaded nickel-manganese oxide composite material by a hydrothermal combination oxidation method, and dissolving nickel nitrate and manganese acetate in 10mL of methanol solution, wherein the molar concentration of nickel ions is 0.5mol/L, and the molar concentration of manganese ions is 0.083 mol/L. And adding 0.6g of PVP into the 10mL of methanol solution, then putting 0.4g of the treated carbon fiber precursor and the methanol mixed solution into an autoclave, placing the autoclave at the temperature of 200 ℃ for hydrothermal treatment for 2h, cooling, carrying out solid-liquid separation, washing with water, and drying at 60 ℃ for 24h to obtain the carbon fiber loaded Ni Mn LDH. And oxidizing for 6h at 500 ℃ in the air atmosphere to obtain the carbon fiber supported nickel-manganese oxide catalyst. The resulting material was characterized and had similar properties as the material of example 1.
Example 3
The preparation method of the carbon fiber loaded nickel-manganese oxide composite material comprises the following steps:
step 1) is the same as in example 1.
Step 2) preparing the carbon fiber loaded nickel-manganese oxide composite material by a hydrothermal combined oxidation method, and dissolving nickel nitrate and manganese acetate in 10mL of methanol solution, wherein the molar concentration of nickel ions is 0.3mol/L, and the molar concentration of manganese ions is 0.052 mol/L. And adding 0.4g of PVP into the 10mL of methanol solution, then putting 0.2g of the treated carbon fiber precursor and the methanol mixed solution into an autoclave, placing the autoclave at the temperature of 100 ℃ for hydrothermal treatment for 10h, cooling, carrying out solid-liquid separation, washing with water, and drying at 60 ℃ for 24h to obtain the carbon fiber loaded Ni Mn LDH. And oxidizing for 3h at 650 ℃ in the air atmosphere to obtain the carbon fiber supported nickel-manganese oxide catalyst. The resulting material was characterized and had similar properties as the material of example 1.
Example 4
The material prepared in example 1 is applied to a zinc-air battery, and the preparation process of the zinc-air battery comprises the following steps:
the liquid zinc-air battery is assembled and tested by adopting the self-made zinc-air battery. 10mg of catalyst was dispersed in 5.6ml of ethanol solution, 32ul of Nafion membrane solution was added and dispersed in an ultrasonic bath, and the uniform ink after complete ultrasonic dispersion was sprayed onto 2 x 2cm carbon paper as an air cathode. A zinc plate having a thickness of 0.5mm was used as the anode. The electrolyte is 6M KOH and 0.2M Zn (CH 3 COO)2. Gas diffusion area of 1 cm2Allowing oxygen in the air to contact the catalyst active sites.
The performance of the battery is tested, and the results are shown in fig. 9-11, which show that the carbon fiber-supported nickel manganese oxide composite material has an ORR half-wave potential of 0.824V and an OER overpotential of 370mV, indicating that the composite material has excellent bifunctional catalytic performance.
The charge and discharge test shows that the material has good stability.
In conclusion, the carbon fiber loaded nickel-manganese oxide composite material is prepared by adopting a method of firstly carrying out electrostatic spinning and then carrying out hydrothermal treatment. The heterogeneous synergistic effect between the nickel manganese oxide and the carbon material and the ordered pore structure in the composite material provide rich catalytic sites, and the high-efficiency and dual-functional characteristics of the catalyst are realized. The carbon fiber loaded nickel-manganese oxide composite material prepared by the method of direct electrostatic spinning after mixing has uneven nickel-manganese oxide loading on the carbon fiber and does not have ORR and OER catalytic performances.
Claims (10)
1. The carbon fiber-loaded nickel-manganese oxide composite material is characterized by being prepared by the following method:
(a) preparing a carbon fiber precursor by an electrostatic spinning method;
(b) preparing a mixed solution of a nickel source and a manganese source, adding polyvinylpyrrolidone into the mixed solution, then adding the carbon fiber precursor, and performing hydrothermal treatment for 2-10h in a reaction kettle at the temperature of 100-;
(c) washing and drying the product obtained in the step (b), and then carrying out oxidation treatment at the oxidation temperature of 500-650 ℃ for 3-6 h.
2. The composite material as claimed in claim 1, wherein in the step (a), polyacrylonitrile and N, N-dimethylformamide are mixed and stirred for 10-14h at 70-80 ℃ to obtain a spinning solution, then the spinning solution is subjected to electrostatic spinning at a voltage of 15-20kV, a distance between a nozzle and a roller is 20-30cm, and a temperature of 20-25 ℃, then the spinning solution is dried for 20-24h at 50-60 ℃, finally the dried spinning solution is placed in a tube furnace under an air atmosphere, and is subjected to pre-oxidation at a heating rate of 1-3 ℃/min until the temperature is increased to 270-300 ℃, and is subjected to heat preservation for 1-2h, and then is subjected to calcination at a heating rate of 3-5 ℃/min under a nitrogen atmosphere after the temperature is increased to 800-900 ℃ and is subjected to heat preservation for 1-2h, and obtaining the carbon fiber precursor.
3. The composite material of claim 1, wherein in the step (b), the concentration of nickel metal ions in the mixed solution is 0.1-0.5mol/L, and the concentration of manganese metal ions is 0.017-0.083 mol/L.
4. The composite material of claim 1, wherein in step (b), the nickel source comprises nickel nitrate, the manganese source comprises manganese acetate, and the solvent of the mixed solution is methanol.
5. The composite material according to claim 1, wherein in step (b), the ratio of polyvinylpyrrolidone, carbon fiber precursor and mixed solution is 0.4-0.6 g: 0.2-0.4 g: 10 mL.
6. The composite material of claim 1, wherein in step (c), the washing agent used for washing is water, and the drying conditions are as follows: drying at 60-100 deg.C for 12-24 hr.
7. The preparation method of the carbon fiber loaded nickel-manganese oxide composite material is characterized by comprising the following steps of:
(a) preparing a carbon fiber precursor by an electrostatic spinning method;
(b) preparing a mixed solution of a nickel source and a manganese source, wherein the concentration of nickel metal ions in the mixed solution is 0.1-0.5mol/L, and the concentration of manganese metal ions in the mixed solution is 0.017-0.083 mol/L; adding polyvinylpyrrolidone into the mixed solution, then adding the carbon fiber precursor, and performing hydrothermal treatment for 2-10h in a reaction kettle at the temperature of 100-;
(c) washing and drying the product obtained in the step (b), and then carrying out oxidation treatment at the oxidation temperature of 500-650 ℃ for 3-6 h.
8. The preparation method according to claim 7, wherein in the step (a), polyacrylonitrile and N, N-dimethylformamide are mixed and stirred for 10-14h at 70-80 ℃ to obtain a spinning solution, then electrostatic spinning is carried out on the spinning solution under the conditions that the voltage is 15-20kV, the distance between a spray head and a roller is 20-30cm, and the temperature is 20-25 ℃, then drying is carried out for 20-24h at 50-60 ℃, finally the dried spinning is put into a tube furnace under the air atmosphere, the temperature is raised to 270-300 ℃ at the temperature raising rate of 1-3 ℃/min, the temperature is preserved for 1-2h for pre-oxidation, then the temperature is raised to 800-900 ℃ at the temperature raising rate of 3-5 ℃/min under the nitrogen atmosphere, the temperature is preserved for 1-2h for calcination, and obtaining the carbon fiber precursor.
9. The method according to claim 1, wherein in the step (b), the nickel source comprises nickel nitrate, the manganese source comprises manganese acetate, and the solvent of the mixed solution is methanol; the proportion of polyvinylpyrrolidone, carbon fiber precursor and mixed solution is 0.4-0.6 g: 0.2-0.4 g: 10 mL; in the step (c), the washing agent used for washing is water, and the drying conditions are as follows: drying at 60-100 deg.C for 12-24 hr.
10. Use of a composite material according to any one of claims 1 to 6 in an air battery.
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