HIGH-ENTROPY NITRIDE CERAMIC FIBER AND PREPARATION METHOD AND USE THEREOF

Abstract

Disclosed are a high-entropy nitride ceramic fiber, and a preparation method and use thereof. The high-entropy ceramic fiber comprises Ti, Hf, Ta, Nb, and Mo; the high-entropy nitride ceramic fiber presents single crystal phase, and each of the elements are uniformly distributed at molecular level. The preparation method of the high-entropy ceramic fiber comprises: mixing a high-entropy ceramic precursor comprising the target metal elements, a spinning aid, and a solvent uniformly to prepare a precursor spinning solution, followed by working procedures of spinning, pyrolyzation, and nitriding to prepare the high-entropy nitride ceramic fiber. The high-entropy nitride ceramic fiber can be used in photocatalysis process of carbon dioxide to prepare methane.

Claims

1-18. (canceled)

19. A high-entropy nitride ceramic fiber, wherein the high-entropy ceramic fiber comprises Ti, Hf, Ta, Nb, and Mo, wherein the high-entropy nitride ceramic fiber is in single crystal phase, and wherein each of the elements are uniformly distributed at molecular level.

20. The high-entropy nitride ceramic fiber according to claim 19, wherein a molar quantity of each of the metal elements in the high-entropy ceramic fiber occupies 5-35% of the total molar quantity of the metal elements; and preferably, the respective metal elements are equimolar.

21. The high-entropy nitride ceramic fiber according to claim 19, wherein the high-entropy ceramic fiber further comprises nitrogen; and wherein the molar quantity of nitrogen is the same as the total molar quantity of Ti, Hf, Ta, Nb, and Mo.

22. The high-entropy nitride ceramic fiber according to claim 19, wherein the high-entropy ceramic fiber further comprises nitrogen and a very small amount of oxygen; and wherein the molar quantity of nitrogen is the same as the total molar quantity of Ti, Hf, Ta, Nb, and Mo.

23. A preparation method of the high-entropy nitride ceramic fiber, wherein the preparation method comprises: mixing a high-entropy ceramic precursor of Ti, Hf, Ta, Nb, and Mo, a spinning aid, and a solvent uniformly to prepare a precursor spinning solution, followed by spinning, pyrolyzation, and nitriding procedures to prepare the high-entropy nitride ceramic fiber.

24. The preparation method of the high-entropy nitride ceramic fiber according to claim 23, wherein the high-entropy ceramic precursor is prepared by: step (1) obtaining metal alkoxide complexes: adding dropwise a complexing agent into metal alkoxides M(OR).sub.n which comprise target metal elements, followed by stirring for 0.1-5 hours to obtain the metal alkoxide complexes; step (2) cohydrolysis: selecting and uniformly mixing the metal alkoxide complexes which comprise different metal elements prepared according to step (1), into which a mixture of water and a monohydric alcohol is added dropwise, followed by refluxing for 1-5 hours, and atmospheric distillation to obtain a metal alkoxide copolymer; step (3) preparing the precursor: mixing the metal alkoxide copolymer prepared in step (2) with allyl-functional novolac resin uniformly, raising the temperature to 50-90° C., and lowering the temperature after 0.5-4 hours of reaction to obtain the high-entropy ceramic precursor.

25. The preparation method of the high-entropy nitride ceramic fiber according to claim 24, wherein in step (1), the molar ratio of the metal alkoxide to the complexing agent is 1:(0.15-0.5) n; wherein the complexing agent is acetylacetone and/or ethyl acetoacetate; wherein in M(OR).sub.n of step (1): when M is Ti or Hf, n is 4; when M is Nb, Ta, or Mo, n is 5; and R is at least one selected from the group consisting of a C1-C6 alkyl and a C1-C6 alkoxy, particularly at least one selected from the group consisting of C1-C4 alkyl and C1-C4 alkoxy, and more particularly at least one selected from the group consisting of ethyl, ethylene glycol diethyl ether, i-Pr, —Pr, and —CH.sub.2CH.sub.2OCH.sub.3.

26. The preparation method of the high-entropy nitride ceramic fiber according to claim 24, wherein in the precursor spinning solution, the mass ratio of the high-entropy ceramic precursor to the spinning aid to the solvent is 1:0.1-1:5-20, preferably 1:0.2-0.5:5-10.

27. The preparation method of the high-entropy nitride ceramic fiber according to claim 24, wherein in step (2), the molar ratio of water to the total metal is 0.8-1.3:1, and the mass ratio of the monohydric alcohol to water is 3-8:1; and wherein the monohydric alcohol is at least one selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol monomethylether, and ethylene glycol ethyl ether.

28. The preparation method of the high-entropy nitride ceramic fiber according to claim 24, wherein in step (3), the ratio of a total molar quantity of the metal elements in the metal alkoxide copolymer to the mass of allyl-functional novolac resin is 1 mol: 18-20 g.

29. The preparation method of the high-entropy nitride ceramic fiber according to claim 23, wherein the nitriding comprises: nitriding the pyrolyzed fiber in ammonia atmosphere at a temperature in the range from 600 to 1000° C. for a period in the range from 0.5 to 5 hours.

30. The preparation method of the high-entropy nitride ceramic fiber according to claim 23, wherein the spinning aid is at least one selected from the group consisting of polymethylmethacrylate, polyvinyl acetate, polyvinyl butyral, and polyvinylpyrrolidone; and wherein the solvent is at least one selected from the group consisting of ethanol, acetone, n-propanol, ethylene glycol monomethylether, and N, N-dimethylformamide.

31. The preparation method of the high-entropy nitride ceramic fiber according to claim 23, wherein the pyrolyzation comprises: raising the temperature to 500-600° C. at a heating rate of 0.5-5° C./min in an inert atmosphere, and maintaining the temperature for 2-4 hours.

32. The preparation method of the high-entropy nitride ceramic fiber according to claim 23, wherein the spinning is at least one selected from the group consisting of blowing spinning, electrospinning, and centrifugal spinning.

33. A method of preparing methane, comprising a step of using high-entropy nitride ceramic fiber according to preparing methane, wherein the high-entropy ceramic fiber comprises Ti, Hf, Ta, Nb, and Mo, wherein the high-entropy nitride ceramic fiber is in single crystal phase, and wherein each of the elements are uniformly distributed at molecular level.

34. The method according to claim 33, wherein a catalyst used in the preparation of methane is the said high-entropy nitride ceramic fiber.

35. The method according to claim 34, wherein a catalytic reaction in which the catalyst participates is photocatalysis; wherein in the photocatalysis, a light source used is visible light; wherein in the photocatalysis, a raw material comprises carbon dioxide; and particularly, the raw material comprises water and carbon dioxide.

36. The method according to claim 33, wherein a molar quantity of each of the metal elements in the high-entropy ceramic fiber occupies 5-35% of the total molar quantity of the metal elements; and preferably, the respective metal elements are equimolar.

37. The method according to claim 33, wherein the high-entropy ceramic fiber further comprises nitrogen; and wherein the molar quantity of nitrogen is the same as the total molar quantity of Ti, Hf, Ta, Nb, and Mo.

38. The method according to claim 33, wherein the high-entropy ceramic fiber further comprises nitrogen and a very small amount of oxygen; and wherein the molar quantity of nitrogen is the same as the total molar quantity of Ti, Hf, Ta, Nb, and Mo.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0061] FIG. 1 is a fiber XRD pattern obtained in Example 2 of the present invention;

[0062] FIG. 2 is a fiber XRD pattern obtained in Example 3 of the present invention;

[0063] FIG. 3 is a fiber XRD pattern obtained in Example 4 of the present invention;

[0064] FIG. 4 is a fiber SEM image obtained in Example 2 of the present invention;

[0065] FIG. 5 is a fiber EDS mapping obtained in Example 3 of the present invention;

[0066] FIG. 6 is a photograph image of the fiber prepared in Example 4 of the present invention; and

[0067] FIG. 7 is a gas chromatogram after photocatalytic reaction in Example 13 of the present invention.

DETAILED DESCRIPTION OF EMBODIMENTS

[0068] The present invention will be further described below in conjunction with particular examples. However, the present invention is not limited to the following examples. Unless otherwise specified, the methods are all conventional ones. The raw materials can all be obtained from open commercial channels unless otherwise specified.

Example 1

[0069] This example provides a general preparation method of high-entropy ceramic precursor, in particular as follows.

[0070] (1) Obtaining Metal Alkoxides:

[0071] Transition metal alkoxides comprising different types of elements are selected. When M in the metal alkoxide is Hf, Nb, Ta, or Mo, the alkoxide is prepared as follows. Metal salt MCl.sub.n or M(NO.sub.3).sub.n is dispersed in a solvent, into which a monohydric alcohol is added dropwise at a temperature in the range from −10° C. to 5° C., followed by adding dropwise of triethylamine, then refluxing for 1-5 hours, and then filtration to obtain a metal alkoxide solution.

[0072] When M in the metal alkoxide is Hf, n is 4.

[0073] When M in the metal alkoxide is Nb, Ta, or Mo, n is 5.

[0074] The molar ratio of the metal salt to monohydric alcohol to triethylamine is 1:(1-2)n:(1-1.5)n.

[0075] The solvent is one or more selected from the group consisting of n-hexane, n-heptane, toluene, xylene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and tert-butyl methyl ether.

[0076] The monohydric alcohol is one or more selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol monomethylether, and ethylene glycol ethyl ether.

[0077] (2) Preparation of Metal Alkoxide Complexes:

[0078] Under the condition from room temperature to 80° C., a complexing agent is added dropwise into the metal alkoxide M(OR).sub.n selected in step (1), followed by stirring for 0.1-5 hours to prepare the metal alkoxide complex.

[0079] The molar ratio of the metal alkoxide to the complexing agent is 1:(0.15-0.5)n.

[0080] When M in the metal alkoxide is Ti or Hf, n is 4.

[0081] When M in metal alkoxide is Nb, Ta, or Mo, n is 5.

[0082] The complexing agent is one or two selected from the group consisting of acetylacetone and ethyl acetoacetate.

[0083] (3) Cohydrolysis:

[0084] The metal alkoxide complexes comprising different metal elements prepared according to step (2) are selected and uniformly mixed, into which a mixture of water and monohydric 35 alcohol is added dropwise at room temperature to 90° C., wherein the molar ratio of water to total metals is 0.8-1.3:1 and the mass ratio of monohydric alcohol to water is 3-8:1, followed by refluxing for 1-5 hours, and atmospheric distillation to obtain a metal alkoxide copolymer.

[0085] The monohydric alcohol is one or more selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol monomethylether, and ethylene glycol ethyl ether.

[0086] (4) Preparation of a Precursor:

[0087] The metal alkoxide copolymer prepared in step (3) is uniformly mixed with allyl phenolic, wherein the ratio of the total molar quantity of the metal elements to the mass of allyl-functional novolac resin is 1 mol: 18-20 g. The temperature is raised to 50-90° C., and reaction is performed for 0.5-4 hours. After that, the temperature is lowered to obtain the high-entropy ceramics precursor.

Example 2

[0088] In this example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0089] 1. Preparation of a high-entropy precursor: the precursor was prepared according to the method of Example 1, with specific steps as follows.

[0090] (1) Obtaining Metal alkoxides: The metal alkoxides were selected from the group consisting of Hf(Oi-Pr).sub.4, Ti(OPr).sub.4, Ta(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, Mo(OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3).sub.5, and Nb(OPr).sub.5, wherein Mo(OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3).sub.5, Hf(Oi-Pr).sub.4, Ta(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, and Nb(OPr).sub.5 were obtained as follows. Metal salts MoCl.sub.5, HfCl.sub.4, TaCl.sub.5, and NbCl.sub.5 were dispersed in n-heptane, respectively, into which ethylene glycol ethyl ether, isopropanol, ethylene glycol monomethylether, and n-propanol were respectively added dropwise at 0° C., followed by respective adding dropwise of triethylamine. After that, the system was refluxed for 2 h, followed by respective filtration to obtain metal alkoxide solutions. The ratios of metal salts MoCl.sub.5, HfCl.sub.4, TaCl.sub.5, and NbCl.sub.5 to the monohydric alcohol to triethylamine were 1:6:5, 1:4:4, 1:10:6, and 1:6:6, respectively.

[0091] (2) Preparation of Metal Alkoxide Complexes:

[0092] At 50° C., acetylacetone was added dropwise into metal alkoxides Hf(Oi-Pr).sub.4, Ti(OPr).sub.4, Ta(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, Mo(OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3).sub.5, and Nb(OPr).sub.5, respectively, followed by stirring for 1 hour.

[0093] The molar ratios of the metal alkoxides Hf(Oi-Pr).sub.4, Ti(OPr).sub.4, Ta(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, Mo(OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3).sub.5, and Nb(OPr).sub.5 to acetylacetone were 1:1.1, 1:0.8, 1:1, 1:2, and 1:1.5, respectively;

[0094] (3) Cohydrolysis:

[0095] The metal alkoxide complexes obtained in step (2) were uniformly mixed in an equal metal molar ratio. A mixed solution of water and n-propanol was added dropwise into the system at 70° C., wherein the molar ratio of water to total metals was 1.2:1, and the mass ratio of n-propanol to water was 8:1. After that, refluxing was performed for 2 hours.

[0096] A metal alkoxide copolymer was obtained by atmospheric distillation.

[0097] (4) Preparation of a Precursor:

[0098] The metal alkoxide copolymer obtained in step (3) was uniformly mixed with allyl-functional novolac resin. The ratio of the total molar quantity of the metal elements in the alkoxide copolymer to the mass of allyl phenolic was 1 mol: 19.5 g. The temperature was raised to 80° C. and reaction was performed for 1 hour. The temperature was then lowered to obtain the high-entropy ceramics precursor.

[0099] 2. Preparation of High-Entropy Nitride Ceramic Fiber

[0100] (1) Preparation of a Spinnable Precursor Solution:

[0101] 30 g of the high-entropy ceramic precursor, 10 g of polyvinylpyrrolidone, and 150 g of ethanol were mixed and stirred to obtain a brown homogenous solution.

[0102] (2) Spinning and Collection:

[0103] Compressed air was used as a gas source, and the precursor solution obtained in step (1) was stretched into nanofiber by means of a blow spinning device. The spinning was performed at the pressure of 0.09 MPa, the feeding speed of 30 mL/h, and the receiving distance of 40 cm.

[0104] (3) Pyrolyzation:

[0105] Nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 1° C./min in nitrogen atmosphere, and was kept for 2 hours to obtain a pyrolyzed fiber.

[0106] (4) Nitriding:

[0107] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the temperature of 800° C. for 2 hours to obtain a high-entropy nitride fiber cotton.

[0108] The XRD pattern of the high-entropy nitride ceramic fiber is shown in FIG. 1. As shown in the figure, the fiber forms a single crystal phase structure, indicating that the high-entropy nitride ceramic was successfully prepared. Its SEM is shown in FIG. 4. As shown in the figure, the diameter of the fiber is rather homogenous. The specific surface area of the fiber was measured to be 6 m.sup.2/g by a specific surface area analyzer.

[0109] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 3

[0110] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0111] (1) Preparation of a Spinnable Precursor Solution:

[0112] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1, and the specific preparation method was the same as that in Example 2.

[0113] 30 g of the high-entropy ceramic precursor, 10 g of polyvinyl butyral, and 285 g of n-propanol were mixed and stirred to obtain a brown homogenous solution.

[0114] (2) Spinning and Collection:

[0115] Compressed nitrogen was used as a gas source, the precursor solution obtained in step (1) was air spun by means of a blow spinning device and stretched into nanofiber at the spinning pressure of 0.06 MPa, the feeding speed of 30 mL/h, and the receiving distance of 40 cm.

[0116] (3) Pyrolyzation:

[0117] The nanofiber collected in step (2) was placed in a heat treatment device, and the temperature was raised to 600° C. at the heating rate of 1.5° C./min in argon atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0118] (4) Nitriding:

[0119] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 900° C. for 2 hours to obtain a high-entropy nitride fiber.

[0120] The XRD pattern of the high-entropy nitride ceramic fiber is shown in FIG. 2. As shown in the figure, the fiber forms a single crystal phase structure, indicating that the high-entropy nitride ceramic has been successfully prepared. The EDS mapping of the fiber shows that all metal elements in the fiber are rather homogenous distributed (FIG. 5).

[0121] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 4

[0122] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0123] 1. Preparation of a high-entropy precursor: the precursor was prepared according to the method of Example 1, with specific steps as follows.

[0124] (1) Obtaining metal alkoxides: The metal alkoxides were selected from the group consisting of Hf(OPr).sub.4, Ti(OPr).sub.4, Ta(OPr).sub.5, Mo(OPr).sub.5, and Nb(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, wherein Hf(OPr).sub.4, Ta(OPr).sub.5, Mo(OPr).sub.5, and Nb(OCH.sub.2CH.sub.2OCH.sub.3)s were obtained as follows. Metal salts HfCl.sub.4, TaCl.sub.5, MoCl.sub.5, and NbCl.sub.5 were dispersed in n-hexane respectively, and monohydric alcohols n-propanol, n-propanol, n-propanol, and ethylene glycol monomethylether were added dropwise at −5° C. respectively, followed by respective adding dropwise of triethylamine. After that, refluxing was performed for 2 hours under heating, and the metal alkoxide solutions were obtained by respective filtration. Therein, the ratios of metal salts HfCl.sub.4, TaCl.sub.5, MoCl.sub.5, and NbCl.sub.5 to the monohydric alcohol to triethylamine were 1:6:5, 1:5:5, 1:10:6, and 1:8:7, respectively.

[0125] (2) Preparation of Metal Alkoxide Complexes:

[0126] At room temperature, acetylacetone was added dropwise into metal alkoxides Hf(OPr).sub.4, Ti(OPr).sub.4, Ta(OPr).sub.5, Mo(OPr).sub.5, and Nb(OCH.sub.2CH.sub.2OCH.sub.3).sub.5, respectively, followed by stirring for 1 h.

[0127] The molar ratios of metal alkoxides Hf(OPr).sub.4, Ti(OPr).sub.4, Ta(OPr).sub.5, Mo(OPr).sub.5, and Nb(OCH.sub.2CH.sub.2OCH.sub.3).sub.5 to acetylacetone were 1:0.5, 1:0.8, 1:1, 1:2, and 1:0.9, respectively.

[0128] (3) Cohydrolysis:

[0129] The metal alkoxide complexes obtained in step (2) were uniformly mixed in equal metal molar ratio. A mixed solution of water and n-propanol was added dropwise into the system at room temperature, wherein the molar ratio of water to total metals was 1:1, and the mass ratio of n-propanol to water was 5:1. After that, refluxing was performed for 2 hours.

[0130] A metal alkoxide copolymer was obtained by atmospheric distillation.

[0131] (4) Preparation of a Precursor:

[0132] The metal alkoxide copolymer obtained in step (3) was uniformly mixed with allyl-functional novolac resin. The ratio of the total molar quantity of the metal elements in the alkoxide copolymer to the mass of allyl-functional novolac resin was 1 mol: 18 g. The temperature was raised to 90° C. and reaction was performed for 3 h. The temperature was then lowered to obtain the high-entropy ceramics precursor.

[0133] 2. Preparation of High-Entropy Nitride Ceramic Fiber

[0134] (1) Preparation of a Spinnable Precursor Solution:

[0135] 30 g of the high-entropy ceramic precursor, 10 g of polyvinyl acetate, and 290 g of ethanol were taken to be mixed and stirred to obtain a brown homogenous solution.

[0136] (2) Spinning and Collection:

[0137] The precursor solution obtained in step (1) was stretched into nanofiber by means of an electrospinning device at the spinning voltage of 10 k, the feeding speed of 40 mL/h, and the receiving distance of 40 cm.

[0138] (3) Pyrolyzation:

[0139] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 1° C./min in argon atmosphere, and 20 was kept for 2 hours to obtain a pyrolyzed fiber.

[0140] (4) Nitriding:

[0141] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and 25 nitrided in ammonia atmosphere at the nitriding temperature of 1000° C. for 2 hours to obtain a high-entropy nitride fiber.

[0142] The XRD pattern of the high-entropy nitride ceramic fiber is shown in FIG. 3, and the photograph image of the fiber is shown in FIG. 6.

[0143] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 5

[0144] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0145] (1) Preparation of a Spinnable Precursor Solution:

[0146] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 2, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=10:35:35:10:10.

[0147] 30 g of the high-entropy ceramic precursor, 10 g of polymethylmethacrylate, and 300 g of ethylene glycol monomethylether were mixed and stirred to obtain a brown homogenous solution.

[0148] (2) Spinning and Collection:

[0149] The precursor solution obtained in step (1) was stretched into nanofiber by means of an electrospinning device at the spinning voltage of 15 kV, the feeding speed of 30 mL/h, and the receiving distance of 45 cm.

[0150] (3) Pyrolyzation:

[0151] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 1.5° C./min in argon atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0152] (4) Nitriding:

[0153] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 800° C. for 2 hours to obtain a high-entropy nitride fiber.

[0154] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000 35° C.

Example 6

[0155] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0156] (1) Preparation of a Spinnable Precursor Solution:

[0157] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 2, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=15:30:35:15:5.

[0158] 30 g of the high-entropy ceramic precursor, 10 g of polyvinyl acetate, and 290 g of ethanol were mixed and stirred to obtain a brown homogenous solution.

[0159] (2) Spinning and collection:

[0160] The precursor solution obtained in step (1) was stretched into fiber by centrifugal spinning at a rotation speed of 1000 r/min, and the receiving distance of 30 cm.

[0161] (3) Pyrolyzation:

[0162] The nanofiber cotton collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 1° C./min in argon atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0163] (4) Nitriding:

[0164] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 1000° C. for 2 hours to obtain a high-entropy nitride fiber.

[0165] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000 35° C.

Example 7

[0166] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0167] (1) Preparation of a Spinnable Precursor Solution:

[0168] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 4, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=20:30:30:15:5.

[0169] 30 g of the high-entropy ceramic precursor, 2 g of polyvinyl butyral, 10 g of polyvinylpyrrolidone, and 600 g of N, N-dimethylformamide were mixed and stirred to obtain a brown homogenous solution.

[0170] (2) Spinning and Collection:

[0171] Compressed argon was used as a gas source, and the precursor solution obtained in step (1) was gas spun by means of a blow spinning device, stretched into nanofiber at the spinning pressure of 0.02 MPa, the feeding speed of 10 mL/h, and the receiving distance of 10 cm.

[0172] (3) Pyrolyzation:

[0173] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 550° C. at the heating rate of 0.5° C./min in nitrogen atmosphere, and kept for 4 hours to obtain a pyrolyzed fiber.

[0174] (4) Nitriding:

[0175] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 600° C. for 0.5 hour to obtain a high-entropy nitride fiber.

[0176] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 8

[0177] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0178] (1) Preparation of a Spinnable Precursor Solution:

[0179] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 4, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=30:5:35:15:15.

[0180] 30 g of the high-entropy ceramic precursor, 8 g of polyvinyl acetate, 7 g of polyvinyl butyral, and 185 g of n-propanol were mixed and stirred to obtain a brown homogenous solution.

[0181] (2) Spinning and Collection:

[0182] Compressed nitrogen was used as a gas source, and the precursor solution obtained in step (1) was stretched into nanofiber by means of a blow spinning device at the spinning pressure of 0.2 MPa, the feeding speed of 60 mL/h, and the receiving distance of 50 cm.

[0183] (3) Pyrolyzation:

[0184] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 3.5° C./min in argon atmosphere, and kept for 3 hours to obtain a pyrolyzed fiber.

[0185] (4) Nitriding:

[0186] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 700° C. for 5 hours to obtain a high-entropy nitride fiber.

[0187] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 9

[0188] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0189] (1) Preparation of a Spinnable Precursor Solution:

[0190] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 4, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=20:15:5:30:30.

[0191] 30 g of the high-entropy ceramic precursor, 2 g of polymethylmethacrylate, 1 g of polyvinyl acetate, and 160 g of ethanol were mixed and stirred to obtain a brown homogenous solution.

[0192] (2) Spinning and Collection:

[0193] The precursor solution obtained in step (1) was stretched into nanofiber by means of an electrospinning device at the spinning voltage of 5 kV, the feeding speed of 10 mL/h, and the receiving distance of 10 cm.

[0194] (3) Pyrolyzation:

[0195] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 500° C. at the heating rate of 1.5° C./min in nitrogen atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0196] (4) Nitriding:

[0197] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 1000° C. for 2.5 hours to obtain a high-entropy nitride fiber.

[0198] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 10

[0199] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0200] (1) Preparation of a Spinnable Precursor Solution:

[0201] A high-entropy ceramics precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 4, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=8:12:30:15:35.

[0202] 30 g of the high-entropy ceramic precursor, 15 g of polymethylmethacrylate, 10 g of ethanol, and 270 g of ethylene glycol monomethylether were mixed and stirred to obtain a brown homogenous solution.

[0203] (2) Spinning and Collection:

[0204] The precursor solution obtained in step (1) was stretched into nanofiber by means of an electrospinning device at the spinning voltage of 10 kV, the feeding speed of 60 mL/h, and the receiving distance of 50 cm.

[0205] (3) Pyrolyzation:

[0206] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 2° C./min in helium atmosphere, and kept for 3 hours to obtain a pyrolyzed fiber.

[0207] (4) Nitriding:

[0208] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 800° C. for 2 hours to obtain a high-entropy nitride fiber.

[0209] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 11

[0210] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0211] (1) Preparation of a Spinnable Precursor Solution:

[0212] A high-entropy ceramic precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 4, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=10:10:30:30:20.

[0213] 30 g of the high-entropy ceramic precursor, 10 g of polyvinyl butyral, 130 g of n-propanol, and 60 g of acetone were mixed and stirred to obtain a brown homogenous solution.

[0214] (2) Spinning and Collection:

[0215] The precursor solution obtained in step (1) was stretched into fiber by centrifugal spinning at a rotation speed of 500 r/min and the receiving distance of 20 cm.

[0216] (3) Pyrolyzation:

[0217] The nanofiber collected in step (2) was placed in a heat treatment device. The temperatures was raised to 600° C. at the heating rate of 1.5° C./min in nitrogen atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0218] (4) Nitriding:

[0219] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 900° C. for 2 hours to obtain a high-entropy nitride fiber.

[0220] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 12

[0221] In this Example, a high-entropy nitride ceramic fiber was prepared by the following method.

[0222] (1) Preparation of a Spinnable Precursor Solution:

[0223] A high-entropy ceramic precursor comprising Ti, Hf, Ta, Nb, and Mo was prepared by the method recited in Example 1. The specific preparation method was the same as that in Example 2, but with the molar percentage ratio between metals during cohydrolysis of the metal alkoxide complexes being selected as Ti:Hf:Ta:Nb:Mo=30:5:35:15:15.

[0224] 30 g of the high-entropy ceramic precursor, 10 g of polyvinyl butyral, and 190 g of ethylene glycol monomethylether were mixed and stirred to obtain a brown homogenous solution.

[0225] (2) Spinning and Collection:

[0226] The precursor solution obtained in step (1) was stretched into nanofiber by a centrifugal spinning at a rotation speed of 5000 r/min and the receiving distance of 100 cm.

[0227] (3) Pyrolyzation:

[0228] The nanofiber collected in step (2) was placed in a heat treatment device. The temperature was raised to 600° C. at the heating rate of 2° C./min in N.sub.2 atmosphere, and kept for 2 hours to obtain a pyrolyzed fiber.

[0229] (4) Nitriding:

[0230] The pyrolyzed fiber prepared in step (3) was placed in a heat treatment device and nitrided in ammonia atmosphere at the nitriding temperature of 1000° C. for 2 hours to obtain a high-entropy nitride fiber.

[0231] The ultra-high temperature performance of the high-entropy nitride ceramic fiber could not be tested in a general laboratory, because it could not melt at a temperature below 3000° C.

Example 13

[0232] This example was mainly to illustrate the catalytic effect of the high-entropy nitride ceramic fiber prepared by the present invention. In the process of preparing CH.sub.4 from CO.sub.2, pure water and pure carbon dioxide gas were used as raw materials and the high-entropy nitride ceramic nanofiber prepared in Example 4 were used as catalyst. A photocatalytic reaction was carried out under the irradiation of a 300 W Xe lamp. The mass ratio of the catalyst to carbon dioxide was 1:83. After reacting for 12 h, the gas in the reaction vessel was detected by gas chromatography. It was found that conversion products of carbon dioxide were generated, with the main product being methane, indicating that the catalyst had high catalytic selectivity.

[0233] FIG. 7 shows the gas chromatography, with peak positions at 0.777 being generated H.sub.2, 2.543 being generated CO, and 4.685 being generated CH.sub.4. As can be seen, the photocatalysis product was mainly CH.sub.4, and the catalytic selectivity was higher than 90%.

INDUSTRIAL APPLICATION

[0234] After adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art.

[0235] 1. The present invention takes a high-entropy ceramics polymer precursor comprising Ti, Hf, Ta, Nb, and Mo with the molar quantity of each of the metal elements accounting for 5-35% of the total molar quantity of the metal elements as a metal source, and employs blowing spinning, electrospinning, or centrifugal spinning as a forming means to prepare high-entropy nitride ceramic fiber. The fiber has the characteristics of homogenous diameter, high specific surface area, etc. The existing forms of high-entropy nitride ceramics are expanded.

[0236] 2. The high-entropy ceramic precursor spinning solution provided by the present invention has the characteristic of adjustable rheology, and while improving the spinning performance, also enables the spinning solution to be hermetically stored at room temperature for more than 3 weeks with a viscosity change rate not exceeding 5%. This reduces restrictions on subsequent procedures (spinning, Pyrolyzation, and nitriding) and further improves spinning efficiency.

[0237] 3. The present invention prepare the high-entropy ceramic fiber by blowing spinning, electrospinning, or centrifugal spinning, which requires simple equipment, convenient operations, and low costs. Continuous fiber cotton or fiber non-woven fabric with controllable average diameters can be obtained, and rapid scale-up production can be achieved.

[0238] 4. In preparation of CH.sub.4 from CO.sub.2 by photocatalytic conversion, the high-entropy nitride fiber prepared by the present invention is characterized by high conversion efficiency, requiring no cocatalyst, easy separation of the catalyst from raw material and products, etc. This is the first time that the high-entropy nitride ceramics are used in the field and explores a new development direction for use of the high-entropy nitride ceramics.