CN112076773A - WS (WS)2Nano-sheet modified TiN nanotube array composite material and preparation method thereof - Google Patents
WS (WS)2Nano-sheet modified TiN nanotube array composite material and preparation method thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 102
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009830 intercalation Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000002687 intercalation Effects 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000006399 behavior Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to WS2A nano-sheet modified TiN nano-tube array composite material and a preparation method thereof. For WS of the present invention2Lithium intercalation treatment is carried out on the powder to obtain metal type WS2Nanosheet, and then preparing the metal type WS2DMF solution of nanoplatelets; metal type WS2Carrying out high-temperature heat treatment on the nanosheet to obtain the semiconductor type WS2The nano-sheet is prepared by the steps of,then preparing semiconductor type WS2DMF solution of nanoplatelets; putting TiN nanotube array material in metal WS2Nanosheet or semiconductor type WS2Sequentially carrying out ultrasonic treatment, soaking and drying in DMF solution of the nano sheet to obtain the metal type WS2Nanosheet or semiconductor type WS2A nano-sheet modified TiN nano-tube array composite material. WS of the present invention2The nano-sheet modified TiN nano-tube array composite material is expected to be widely applied in the field of electrocatalysis.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to WS2A nano-sheet modified TiN nano-tube array composite material and a preparation method thereof.
Background
Since the research shows that two-dimensional graphene is mechanically stripped in 2004 and the Nobel physics awards in 2010, a two-dimensional material, a newly-developed two-dimensional MoS field, is rapidly developed2And WS2Particularly prominent. Two-dimensional MS2(M ═ Mo, W) as a graphene-like material, stacked together by weak van der waals interactions between layers, which allows the material to be experimentally obtained as a few-or single-layer two-dimensional MS2Nanosheets. Two-dimensional MS2The nano-sheet has very large specific surface area and extremely high surface atomic ratio, and meanwhile, compared with graphene (intrinsic graphene has almost no catalytic activity), the two-dimensional MS2The nanosheet shows abundant electrical behaviors, makes up for the limitation of the application of graphene in the field of electrocatalysis, and becomes a hot point of recent research. On the other hand, the titanium nitride nano material hasHas good electrocatalytic activity, conductivity, biocompatibility and the like, and is low in price. Based on this, the present invention designs a WS2The nano sheet is compounded with the titanium nitride nanotube array to obtain the novel nano composite material.
Disclosure of Invention
In order to improve the MS in the prior art2The electrical conductivity and biocompatibility of the nano material, the object of the present invention is to provide a WS2A nano-sheet modified TiN nano-tube array composite material and a preparation method thereof. WS of the present invention2Nano-sheet modified TiN nanotube array composite material with WS2The nano-sheet and titanium nitride nanotube array material has good electrocatalytic activity, conductivity and biocompatibility, is expected to be applied to the field of electrocatalysis, and the preparation process of the nano-composite material is simple and feasible, and has wide practical application value and industrial production prospect.
The invention is realized by the following technical scheme:
WS (WS)2The preparation method of the nano-sheet modified TiN nano-tube array composite material specifically comprises the following steps:
(1) by WS2Grinding the block as raw material by mechanical ball milling method to obtain WS2Powder;
(2) in a glove box in an anhydrous and oxygen-free environment, under the inert gas environment of nitrogen, argon or helium, adopting n-hexane solution of butyl lithium to react WS2Performing lithium intercalation treatment on the powder;
(3) intercalating treated WS with lithium2Transferring the powder into deionized water, and performing ultrasonic treatment to obtain peeled WS2The aqueous solution is then centrifuged to obtain the metal type WS2Nanosheet, and then redispersing the nanosheet in DMF solvent to obtain the metal type WS2DMF solution of nanoplatelets;
(4) the metal type WS in the step (3) is treated2Carrying out high-temperature heat treatment on the nanosheets under the protection of inert gas such as nitrogen, argon or helium to obtain the semiconductor type WS2Nanosheets and then coupling said semiconducting WS2Nanosheet dispersionAdding into DMF solvent to obtain semiconductor type WS2DMF solution of nanoplatelets;
(5) putting TiN nanotube array material into the metal type WS in the step (3)2DMF solution of nanosheets or semiconducting WS in step (4)2Sequentially carrying out ultrasonic treatment, soaking and drying in DMF solution of the nano sheet to obtain the metal type WS2Nanosheet or semiconductor type WS2A nano-sheet modified TiN nano-tube array composite material.
Preferably, the mechanical ball milling method in step (1) is specifically operated as follows: the large size WS of 6 μm in size2Placing the block in a ball milling tank, and grinding at room temperature for 120min at 20Hz to obtain WS with a size of less than 2 μm2And (3) powder.
Preferably, the purity of the inert gas in the step (2) is 99.99%, and the molar concentration of the butyl lithium in the n-hexane solution of the butyl lithium is 2.5moL/L per 20mg of WS2The volume of butyllithium required was 500. mu.L, WS2And putting the powder into the n-hexane solution of the butyl lithium for lithium intercalation treatment.
Preferably, WS in step (3)2The mass-volume ratio of the powder to the deionized water is 10mg:20mL, and the ultrasonic treatment time is 20 min; the centrifugal separation is specifically operated as follows: first, the peeled WS2Centrifuging the water solution at 600-6000rpm for 10min, collecting the supernatant, centrifuging at 10000rpm for 10min to obtain precipitate as metal type WS2Nanosheets; said metal type WS2The size of the nano-sheet is 100nm-2 μm.
Preferably, said metallic WS in step (3)2Metal-type WS in DMF solution of nanosheets2The mass fraction of the nano sheet is 1mg/mL, and the semiconductor type WS is obtained in the step (4)2Semiconducting WS in DMF solution of nanosheets2The mass fraction of the nano-sheets is 1 mg/mL.
Preferably, the purity of the inert gas in the step (4) is 99.9%, the temperature of the high-temperature heat treatment is 250 ℃, and the time of the high-temperature heat treatment is 60 min.
Preferably, the time of the ultrasonic treatment in the step (5) is 10 s; the soaking time is 2 min; the drying temperature is 60 ℃, and the drying time is 300 min.
The invention also aims to provide WS prepared by the method2The TiN nanotube array composite material modified by the nano-sheets, wherein TiN nanotubes vertically grow on a Ti sheet substrate, and the WS2The nano-sheet is loaded on the upper surface of the TiN nano-tube, and the TiN nano-tube has an outer diameter of 60-90nm and an inner diameter of 20-30 nm.
Preferably, said WS2The nano sheet is a metal type WS2Nanosheet or semiconductor type WS2Nanosheets.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses ultrasonic stripping to strip large-size WS2Conversion of powder into two-dimensional WS2The nanosheet has a large specific surface area and a very high surface atomic ratio, and shows abundant electrical behavior and high catalytic activity; the titanium nitride nano material has good electrocatalytic activity, conductivity, biocompatibility and the like, and the price is low, and the invention leads the two-dimensional WS to be2The nano sheet and TiN nano tube array material are compounded by a simple method to obtain the novel WS2Nano-sheet modified TiN nanotube array composite material with WS2The nano-sheet and titanium nitride nanotube array material has good electrocatalytic activity, conductivity and biocompatibility, and is expected to be applied to the field of electrocatalysis.
(2) The preparation method has the advantages of simple and feasible preparation process, easily obtained raw materials, wide practical application value and wide industrial production prospect.
Drawings
FIG. 1 shows WS according to the present invention2And the structural schematic diagram of the nano-sheet modified TiN nano-tube array composite material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
WS (WS)2The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized by comprising the following steps:
(1) by WS2Grinding block with mechanical ball milling method to obtain large size WS of 6 μm2Placing the block in a ball milling tank, and grinding at room temperature for 120min at 20Hz to obtain WS with a size of less than 2 μm2Powder;
(2) in a glove box in an anhydrous and oxygen-free environment, under an inert gas atmosphere of nitrogen (with a purity of 99.9%), according to the WS content of 20mg2The volume of butyllithium required was 500. mu.L, WS2Placing the powder in the n-hexane solution of butyl lithium for room-temperature soaking for lithium intercalation treatment, wherein the molar concentration of butyl lithium in the n-hexane solution of butyl lithium is 2.5 moL/L;
(3) intercalating treated WS with lithium2Transferring 10mg of the powder into 20mL of deionized water, and then performing ultrasonic treatment for 20min to obtain the stripped WS2Aqueous solution, and then stripping WS2And (3) carrying out centrifugal separation on the aqueous solution: first, the peeled WS2Centrifuging the aqueous solution at 6000rpm for 10min, collecting the supernatantCentrifuging the supernatant at 10000rpm for 10min to obtain precipitate as metal type WS2Nanosheets, the metallic WS2The average size of the nano-sheets is 100 nm; then the metal type WS is treated2Re-dispersing the nano-sheet into a DMF solvent to obtain the metal type WS2DMF solution with the mass fraction of the nano-sheets being 1 mg/mL;
(4) putting TiN nanotube array material into the metal type WS in the step (3)2Sequentially carrying out ultrasonic treatment for 10s, soaking for 2min and drying at 60 ℃ for 300min in DMF solution of the nano sheet to obtain the metal type WS2A nano-sheet modified TiN nano-tube array composite material.
As shown in FIG. 1, the metal type WS prepared in this example2The TiN nanotube array composite material modified by the nano-sheets, wherein TiN nanotubes vertically grow on a Ti sheet substrate, and the WS2The nano-sheet is loaded on the upper surface of the TiN nano-tube, and the TiN nano-tube has an outer diameter of 60-90nm and an inner diameter of 20-30 nm.
Example 2
WS (WS)2The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized by comprising the following steps:
(1) by WS2Grinding block with mechanical ball milling method to obtain large size WS of 6 μm2Placing the block in a ball milling tank, and grinding at room temperature for 120min at 20Hz to obtain WS with a size of less than 2 μm2Powder;
(2) in a glove box in an anhydrous and oxygen-free environment, under an inert gas atmosphere of nitrogen (with a purity of 99.9%), according to the WS content of 20mg2The volume of butyllithium required was 500. mu.L, WS2Placing the powder in the n-hexane solution of butyl lithium for room-temperature soaking for lithium intercalation treatment, wherein the molar concentration of butyl lithium in the n-hexane solution of butyl lithium is 2.5 moL/L;
(3) intercalating treated WS with lithium2Transferring 10mg of the powder into 20mL of deionized water, and then performing ultrasonic treatment for 20min to obtain the stripped WS2Aqueous solution ofThen peeled WS2And (3) carrying out centrifugal separation on the aqueous solution: first, the peeled WS2Centrifuging the water solution at 3000rpm for 10min, collecting supernatant, centrifuging at 10000rpm for 10min to obtain precipitate as metal type WS2Nanosheets, the metallic WS2The average size of the nano-sheets is 500 nm; then the metal type WS is treated2Re-dispersing the nano-sheet into a DMF solvent to obtain the metal type WS2DMF solution with the mass fraction of the nano-sheets being 1 mg/mL;
(4) the metal type WS in the step (3) is treated2Carrying out high-temperature heat treatment at 250 ℃ for 60min under the protection of inert gas with nitrogen (the purity is 99.9%) to obtain the semiconductor type WS2Nanosheets and then coupling said semiconducting WS2Dispersing the nano-sheet into DMF solvent to obtain semiconductor type WS2DMF solution with the mass fraction of the nano-sheets being 1 mg/mL;
(5) putting TiN nanotube array material on the semiconductor type WS in the step (4)2Then ultrasonic treatment is carried out for 10s, the obtained product is soaked for 2min and dried for 300min at the temperature of 60 ℃ in sequence to obtain the semiconductor type WS2A nano-sheet modified TiN nano-tube array composite material.
As shown in FIG. 1, the semiconductor type WS prepared in this example2The TiN nanotube array composite material modified by the nano-sheets, wherein TiN nanotubes vertically grow on a Ti sheet substrate, and the WS2The nano-sheet is loaded on the upper surface of the TiN nano-tube, and the TiN nano-tube has an outer diameter of 60-90nm and an inner diameter of 20-30 nm.
Example 3
WS (WS)2The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized by comprising the following steps:
(1) by WS2Grinding block with mechanical ball milling method to obtain large size WS of 6 μm2Placing the block in a ball milling tank, and grinding at room temperature for 120min at 20Hz to obtain WS with a size of less than 2 μm2Powder;
(2) in thatIn a glove box in an anhydrous and oxygen-free environment, under an inert gas atmosphere of argon (with the purity of 99.9 percent), WS is added according to the proportion of 20mg2The volume of butyllithium required was 500. mu.L, WS2Placing the powder in the n-hexane solution of butyl lithium for room-temperature soaking for lithium intercalation treatment, wherein the molar concentration of butyl lithium in the n-hexane solution of butyl lithium is 2.5 moL/L;
(3) intercalating treated WS with lithium2Transferring 10mg of the powder into 20mL of deionized water, and then performing ultrasonic treatment for 20min to obtain the stripped WS2Aqueous solution, and then stripping WS2And (3) carrying out centrifugal separation on the aqueous solution: first, the peeled WS2Centrifuging the water solution at 600rpm for 10min, collecting supernatant, centrifuging at 10000rpm for 10min to obtain precipitate as metal type WS2Nanosheets, the metallic WS2The average size of the nanosheets is 2 μm; then the metal type WS is treated2Re-dispersing the nano-sheet into a DMF solvent to obtain the metal type WS2DMF solution with the mass fraction of the nano-sheets being 1 mg/mL;
(4) the metal type WS in the step (3) is treated2Carrying out high-temperature heat treatment at 250 ℃ for 60min under the protection of inert gas with nitrogen (the purity is 99.9%) to obtain the semiconductor type WS2Nanosheets and then coupling said semiconducting WS2Dispersing the nano-sheet into DMF solvent to obtain semiconductor type WS2DMF solution with the mass fraction of the nano-sheets being 1 mg/mL;
(5) putting TiN nanotube array material on the semiconductor type WS in the step (4)2Then ultrasonic treatment is carried out for 10s, the obtained product is soaked for 2min and dried for 300min at the temperature of 60 ℃ in sequence to obtain the semiconductor type WS2A nano-sheet modified TiN nano-tube array composite material.
As shown in FIG. 1, the semiconductor type WS prepared in this example2The TiN nanotube array composite material modified by the nano-sheets, wherein TiN nanotubes vertically grow on a Ti sheet substrate, and the WS2The nano-sheet is loaded on the upper surface of the TiN nano-tube, and the TiN nano-tube has an outer diameter of 60-90nm and an inner diameter of 20-30 nm.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. WS (WS)2The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized by comprising the following steps:
(1) by WS2Grinding the block as raw material by mechanical ball milling method to obtain WS2Powder;
(2) in a glove box in an anhydrous and oxygen-free environment, under the inert gas environment of nitrogen, argon or helium, adopting n-hexane solution of butyl lithium to react WS2Performing lithium intercalation treatment on the powder;
(3) intercalating treated WS with lithium2Transferring the powder into deionized water, and performing ultrasonic treatment to obtain peeled WS2The aqueous solution is then centrifuged to obtain the metal type WS2Nanosheet, and then redispersing the nanosheet in DMF solvent to obtain the metal type WS2DMF solution of nanoplatelets;
(4) the metal type WS in the step (3) is treated2Carrying out high-temperature heat treatment on the nanosheets under the protection of inert gas such as nitrogen, argon or helium to obtain the semiconductor type WS2Nanosheets and then coupling said semiconducting WS2Dispersing the nano-sheet into DMF solvent to obtain semiconductor type WS2DMF solution of nanoplatelets;
(5) putting TiN nanotube array material into the metal type WS in the step (3)2DMF solution of nanosheets or semiconducting WS in step (4)2Sequentially carrying out ultrasonic treatment, soaking and drying in DMF solution of the nano sheet to obtain the metal type WS2Nanosheet or semiconductor type WS2A nano-sheet modified TiN nano-tube array composite material.
2. Root of herbaceous plantA WS according to claim 12The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized in that the mechanical ball milling method in the step (1) is specifically operated as follows: the large size WS of 6 μm in size2Placing the block in a ball milling tank, and grinding at room temperature for 120min at 20Hz to obtain WS with a size of less than 2 μm2And (3) powder.
3. WS according to claim 12The preparation method of the nano-sheet modified TiN nanotube array composite material is characterized in that the purity of the inert gas in the step (2) is 99.99%, the molar concentration of butyl lithium in n-hexane solution of the butyl lithium is 2.5moL/L, and the WS per 20mg2The volume of butyllithium required was 500. mu.L, WS2And putting the powder into the n-hexane solution of the butyl lithium for lithium intercalation treatment.
4. WS according to claim 12The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized in that the WS in the step (3)2The mass-volume ratio of the powder to the deionized water is 10mg:20mL, and the ultrasonic treatment time is 20 min; the centrifugal separation is specifically operated as follows: first, the peeled WS2Centrifuging the water solution at 600-6000rpm for 10min, collecting the supernatant, centrifuging at 10000rpm for 10min to obtain precipitate as metal type WS2Nanosheets; said metal type WS2The size of the nano-sheet is 100nm-2 μm.
5. WS according to claim 12The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized in that the metal type WS in the step (3)2Metal-type WS in DMF solution of nanosheets2The mass fraction of the nano sheet is 1mg/mL, and the semiconductor type WS is obtained in the step (4)2Semiconducting WS in DMF solution of nanosheets2The mass fraction of the nano-sheets is 1 mg/mL.
6. WS according to claim 12The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized in that the purity of the inert gas in the step (4) is 99.9%, the high-temperature heat treatment temperature is 250 ℃, and the high-temperature heat treatment time is 60 min.
7. WS according to claim 12The preparation method of the nano-sheet modified TiN nano-tube array composite material is characterized in that the ultrasonic treatment time in the step (5) is 10 s; the soaking time is 2 min; the drying temperature is 60 ℃, and the drying time is 300 min.
8. WS prepared by a process according to any one of claims 1 to 72The TiN nanotube array composite material modified by the nano-sheets is characterized in that TiN nanotubes vertically grow on a Ti sheet substrate, and the WS is2The nano-sheet is loaded on the upper surface of the TiN nano-tube, and the TiN nano-tube has an outer diameter of 60-90nm and an inner diameter of 20-30 nm.
9. WS according to claim 82The TiN nanotube array composite material modified by the nano-sheet is characterized in that the WS2The nano sheet is a metal type WS2Nanosheet or semiconductor type WS2Nanosheets.
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