CN111945132B - Vertically-grown niobium disulfide nanosheet and preparation method and application thereof - Google Patents
Vertically-grown niobium disulfide nanosheet and preparation method and application thereof Download PDFInfo
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- VRSMQRZDMZDXAU-UHFFFAOYSA-N bis(sulfanylidene)niobium Chemical compound S=[Nb]=S VRSMQRZDMZDXAU-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002135 nanosheet Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- 239000004744 fabric Substances 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 68
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
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- 238000006243 chemical reaction Methods 0.000 claims description 49
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- 238000011144 upstream manufacturing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010431 corundum Substances 0.000 description 11
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/23—
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a vertically-grown niobium disulfide nanosheet and a preparation method and application thereof, and belongs to the technical field of preparation of electrochemical catalytic hydrogen production materials. The preparation method takes niobium pentachloride and sulfur powder as precursors, and the niobium pentachloride and the sulfur powder grow for 20 to 40min at 850 to 950 ℃ in an inert atmosphere, wherein the distance between the sulfur powder and the carbon cloth substrate is controlled to be 20 to 21cm, so that the structure-controllable vertically-grown niobium disulfide nanosheet can be successfully prepared on the carbon cloth substrate; meanwhile, the carbon cloth is cheap as a growing substrate, the chemical vapor deposition method is good in operation controllability and easy to introduce into actual industrial production, and therefore the preparation method has wide application prospects in the green chemical industry. The vertically-grown niobium disulfide nanosheet provided by the invention is coupled with the carbon cloth substrate, the coupling structure is beneficial to effective charge transmission and active site increase, and experiments prove that the prepared vertically-grown niobium disulfide nanosheet has better electrocatalytic activity and stability when being used as an electrochemical hydrogen production catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of electrochemical catalytic hydrogen production materials, and particularly relates to a vertically-grown niobium disulfide nanosheet and a preparation method and application thereof.
Background
The fuel hydrogen without carbon emission is considered as an effective green energy source in the future, and can solve the problems of sustainable development and energy safety. In addition, hydrogen is also a key contributor in the oil refining industry, the chemical industry, and the electronics industry. The efficiency of hydrogen energy generation is improved at present. There are two main approaches to improving the catalytic performance of Hydrogen Evolution Reactions (HER): charge transport efficiency and effective active sites. Due to high electrical conductivity and strong catalytic activity, platinum-based catalysts are one of the most effective electrocatalysts, however, the expensive price thereof requires the urgent need to develop a new alternative material. In recent years, two-dimensional (2D) transition metal chalcogenides have attracted considerable research interest due to their low cost and unique properties.
Wherein the two-dimensional (2D) niobium disulfide (NbS) 2 ) The near-zero gibbs free energy and the stability of the super-strong acid electrolyte have led to great research interest in hydrogen evolution reactions. It has been reported that different forms of NbS can be prepared 2 Nanowires, nanotubes, and thin films. More recently, ago et al used chemical vapor deposition to deposit Si/SiO 2 Successfully prepares single crystal NbS with controllable direction 2 And (4) crystal domains. However, nano-sized niobium disulfide (NbS) 2 ) The controlled preparation of materials remains one of the challenges facing today.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a vertically grown niobium disulfide nanosheet, and a preparation method and application thereof. Compared with other technologies, the preparation method is simpler and more controllable in technological parameters, the niobium disulfide nanosheet prepared by the preparation method has a vertical-growth uniform and stable structure, and meanwhile, the charge transmission efficiency of the material is effectively improved, so that the preparation method can be applied to electrocatalysis.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a vertically-grown niobium disulfide nanosheet, which comprises the following steps: depositing niobium pentachloride and sulfur powder serving as precursors on a carbon cloth substrate by adopting a chemical vapor deposition method to obtain vertically grown niobium disulfide nanosheets;
wherein, the niobium pentachloride is arranged below the carbon cloth substrate, the sulfur powder is arranged at the upstream of the niobium pentachloride, and the distance between the sulfur powder and the center of the carbon cloth substrate is 20-21 cm.
Preferably, the preparation method specifically comprises the following steps:
placing the reaction boat with the niobium pentachloride in a constant temperature reaction area of a vacuum tube furnace, placing a carbon cloth substrate above the reaction boat, and leaving air vents at two ends of the reaction boat;
and (3) placing sulfur powder at the upstream position of the airflow of the vacuum tube furnace, wherein the distance between the sulfur powder and the center of the carbon cloth substrate above the reaction boat is 20-21 cm, and obtaining the vertically-grown niobium disulfide nanosheets on the carbon cloth substrate by a chemical vapor deposition method in an inert atmosphere.
Preferably, a chemical vapor deposition method is adopted, the reaction temperature is increased to 850-950 ℃, and the heat preservation time is 20-40 min; wherein the heating rate is 30 ℃/min.
Preferably, the mass ratio of the niobium pentachloride to the sulfur powder is (1-8): 10.
Further preferably, the carbon cloth substrate is subjected to a pretreatment operation before use, specifically comprising: and ultrasonically cleaning the carbon cloth substrate in absolute ethyl alcohol and deionized water respectively, and then drying.
Further preferably, the reaction boat and the reaction container are subjected to a pretreatment operation before use, specifically comprising: the reaction boat and the reaction container are respectively cleaned in absolute ethyl alcohol, isopropanol and acetone by ultrasonic waves, dried and presintered in a vacuum tube furnace, wherein the presintering temperature is 200 ℃, and the presintering time is 30min.
Further preferably, the inert gas flow rate of the inert atmosphere is 50 to 200sccm.
The invention also discloses a vertically grown niobium disulfide nanosheet prepared by the preparation method, wherein the size width of the vertically grown niobium disulfide nanosheet is 1-3 microns.
The invention also discloses application of the vertically-grown niobium disulfide nanosheet as an electrochemical hydrogen production catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a vertically-grown niobium disulfide nanosheet, which takes niobium pentachloride and sulfur powder as precursors, and realizes the successful preparation of the vertically-grown niobium disulfide nanosheet on a carbon cloth substrate by placing the sulfur powder at the upstream of the niobium pentachloride and controlling the distance between the sulfur powder and the carbon cloth substrate to be 20-21 cm. The preparation method has the following advantages:
(1) According to the invention, niobium pentachloride is used as the precursor, the concentration of the precursor is effectively increased, so that the reaction is more sufficient, the reaction efficiency is improved, and in experiments, the reaction concentration of a sulfur atmosphere can be made to be proper at a proper position by respectively controlling the positions of sulfur powder and niobium pentachloride through two quartz boats, so that the vertically grown niobium disulfide nanosheet and carbon cloth are coupled to form a more compact structure and have higher verticality, so that a larger specific surface area is provided, and the number of active sites is greatly exposed.
(2) The method of the invention is beneficial to preparing the vertically-grown niobium disulfide nanosheets with small size and large number by adjusting the reaction temperature as the growth parameter, so that the charge diffusion path is short and the charge transfer can be effectively promoted.
(3) The vertically-grown niobium disulfide nanosheet provided by the invention is simple in preparation process and is expected to be introduced into actual industrial production, so that the vertically-grown niobium disulfide nanosheet has a wide application prospect in the green chemical industry.
The invention also discloses a vertically grown niobium disulfide nanosheet prepared by the preparation method, and the vertically grown niobium disulfide (NbS) 2 ) In the nanosheets, nbS 2 The charge transmission efficiency can be effectively improved by directly growing on the conductive substrate. Experiments show that the prepared vertically-grown niobium disulfide nanosheet is 2D-NbS 2 The structure has the size of 1-3 microns, and the overpotential of the electrocatalyst is about 464mV.
The invention also discloses application of the vertically-grown niobium disulfide nanosheet as an electrochemical hydrogen production catalyst. By coupling vertically grown niobium disulfide nanosheets with a carbon cloth substrate, high efficiency HER performance is achieved by promoting a charge transfer process and increasing the number of effective active sites, thereby achieving NbS 2 As a novel electrochemical auxiliary catalyst, nbS is promoted 2 The electrochemical application performance of the material is expanded to NbS 2 In electrocatalysis of materialsThe practical application of (1).
Drawings
FIG. 1 is an XRD pattern of vertically grown niobium disulfide nanosheets prepared in examples 1-3 of the present invention;
FIG. 2 is an SEM image of vertically grown niobium disulfide nanosheets prepared in examples 1-3 of the present invention; wherein (a) is example 1, (b) is example 2, and (c) is example 3;
fig. 3 is a hydrogen production performance diagram of vertically-grown niobium disulfide nanosheets prepared in embodiment 2 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, 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. 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a vertically-grown niobium disulfide nanosheet, which comprises the following steps:
step 1, pretreating a carbon cloth substrate to obtain a pretreated carbon cloth substrate;
step 2, paving the pretreated carbon cloth substrate above the reaction boat, reserving air vents at two ends of the reaction boat, and placing the reaction boat in a central constant-temperature reaction area of the tubular furnace;
and (3) respectively placing the niobium pentachloride and the sulfur powder in a reaction container, placing the reaction container at the upstream of the airflow, and ensuring that the sulfur powder is at the upstream of the niobium pentachloride at a position 20-21 cm away from the reaction boat in the step 2. And then, in the inert gas atmosphere, raising the temperature in the vacuum tube furnace to 850-950 ℃, and preserving the temperature for 20-40 min, namely depositing on a carbon cloth substrate to obtain the vertically grown niobium disulfide nanosheet.
Wherein the mass ratio of the niobium pentachloride to the sulfur powder is (1-8) to 10; the pretreatment steps of the reaction boat and the reaction container in the step 1 are as follows: ultrasonically cleaning a reaction boat and a reaction container in absolute ethyl alcohol, isopropanol and acetone respectively, drying, and presintering in a vacuum tube furnace, wherein the presintering temperature is 200 ℃, and the presintering time is 30min; the pretreatment step of the carbon cloth substrate in the step 1 is as follows: ultrasonically cleaning a carbon cloth substrate in absolute ethyl alcohol and deionized water respectively, and drying to obtain a pretreated carbon cloth substrate; in the step 2, the heating rate is 30 ℃/min, and the argon flow is 50-200 sccm; the reaction boat is a corundum boat, and the reaction vessel is a quartz boat.
The niobium disulfide nanosheet prepared by the method is of a vertical growth structure, and the size is 1-3 mu m.
The invention will be further illustrated and described with reference to specific examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of vertically-grown niobium disulfide nanosheets comprises the following steps:
step 1, pretreating a carbon cloth substrate: ultrasonically cleaning a carbon cloth substrate with the size of 1.8cm multiplied by 4.5cm in absolute ethyl alcohol and deionized water for 10min and 5min respectively, and then drying in a 60 ℃ drying oven to obtain a pretreated carbon cloth substrate;
and 2, weighing 150mg of niobium pentachloride, placing the niobium pentachloride in a cleaned quartz boat, and placing the quartz boat filled with the powder in a preset position at the upstream of the airflow. Then laying the pretreated carbon cloth substrate above the corundum boat, and reserving air vents at both ends of the reaction boat;
weighing 500mg of sulfur powder and stacking the sulfur powder in quartz boats, then placing the corundum boat and the two quartz boats in a tube furnace at a distance of 20 cm, heating the tube furnace to 850 ℃ at a heating rate of 30 ℃/min under the condition that the flow of argon is 200sccm, naturally cooling to room temperature after growing for 40min, and preparing the vertically-grown niobium disulfide nanosheets on a carbon cloth substrate; and placing the carbon cloth substrate with the vertically-grown niobium disulfide nanosheets in a sample box for dry storage to prevent reaction with oxygen.
Example 2
A preparation method of vertically-grown niobium disulfide nanosheets comprises the following steps:
step 1, pretreating a carbon cloth substrate: ultrasonically cleaning a carbon cloth substrate with the size of 1.8cm multiplied by 4.5cm in absolute ethyl alcohol and deionized water for 10min and 5min respectively, and then drying in a 60 ℃ drying oven to obtain a pretreated carbon cloth substrate;
and 2, weighing 150mg of niobium pentachloride, placing the niobium pentachloride in a cleaned quartz boat, and placing the quartz boat filled with the powder in a preset position at the upstream of the airflow. Then laying the pretreated carbon cloth substrate above the corundum boat, and reserving air vents at both ends of the reaction boat;
weighing 500mg of sulfur powder and stacking the sulfur powder in quartz boats, then placing the corundum boat and the two quartz boats in a tube furnace at a distance of 20.5 cm, heating the tube furnace to 900 ℃ at a heating rate of 30 ℃/min under the condition that the argon flow is 200sccm, growing for 40min, naturally cooling to room temperature, and preparing the vertically-grown niobium disulfide nanosheet on a carbon cloth substrate; and placing the carbon cloth substrate with the vertically-grown niobium disulfide nanosheets in a sample box for dry storage to prevent reaction with oxygen.
Example 3
A preparation method of vertically-grown niobium disulfide nanosheets comprises the following steps:
step 1, pretreating a carbon cloth substrate: ultrasonically cleaning a carbon cloth substrate with the size of 1.8cm multiplied by 4.5cm in absolute ethyl alcohol and deionized water for 10min and 5min respectively, and then drying in a 60 ℃ drying oven to obtain a pretreated carbon cloth substrate;
and 2, weighing 150mg of niobium pentachloride, placing the niobium pentachloride in a cleaned quartz boat, and placing the quartz boat filled with the powder in a preset position at the upstream of the airflow. Then laying the pretreated carbon cloth substrate above the corundum boat, and reserving air vents at both ends of the reaction boat;
weighing 500mg of sulfur powder and stacking the sulfur powder in quartz boats, then placing the corundum boat and the two quartz boats in a tube furnace at a distance of 21cm, heating the tube furnace to 950 ℃ at a heating rate of 30 ℃/min under the condition that the argon flow is 200sccm, growing for 40min, naturally cooling to room temperature, and preparing the vertically-grown niobium disulfide nanosheets on a carbon cloth substrate; and placing the carbon cloth substrate with the vertically-grown niobium disulfide nanosheets in a sample box for dry storage to prevent reaction with oxygen.
Example 4
A preparation method of vertically-grown niobium disulfide nanosheets comprises the following steps:
step 1, pretreating a carbon cloth substrate: ultrasonically cleaning a carbon cloth substrate with the size of 1.8cm multiplied by 4.5cm in absolute ethyl alcohol and deionized water for 10min and 5min respectively, and then drying in a 60 ℃ drying oven to obtain a pretreated carbon cloth substrate;
and 2, weighing 50mg of niobium pentachloride, placing the niobium pentachloride in a cleaned quartz boat, and placing the quartz boat filled with the powder in a preset position at the upstream of the airflow. Then laying the pretreated carbon cloth substrate above the corundum boat, and reserving air vents at both ends of the reaction boat;
weighing 500mg of sulfur powder and stacking the sulfur powder in quartz boats, then placing the corundum boat and the two quartz boats in a tubular furnace, adjusting the distance to 20 cm, heating the tubular furnace to 950 ℃ at the heating rate of 30 ℃/min under the condition that the argon flow is 50sccm, growing for 20min, naturally cooling to room temperature, and preparing the vertically-grown niobium disulfide nanosheets on a carbon cloth substrate; and placing the carbon cloth substrate with the vertically-grown niobium disulfide nanosheets in a sample box for dry storage to prevent reaction with oxygen.
Example 5
A preparation method of vertically-grown niobium disulfide nanosheets comprises the following steps:
step 1, pretreating a carbon cloth substrate: ultrasonically cleaning a carbon cloth substrate with the size of 1.8cm multiplied by 4.5cm in absolute ethyl alcohol and deionized water for 10min and 5min respectively, and then drying in a 60 ℃ drying oven to obtain a pretreated carbon cloth substrate;
and 2, weighing 240mg of niobium pentachloride, placing the niobium pentachloride in a cleaned quartz boat, and placing the quartz boat filled with the powder in a preset position at the upstream of the airflow. Then, paving the pretreated carbon cloth substrate above the corundum boat, and simultaneously keeping vent holes at two ends of the reaction boat;
weighing 300mg of sulfur powder and stacking the sulfur powder in quartz boats, then placing the corundum boat and the two quartz boats in a tube furnace, adjusting the distance to 20.5 cm, heating the tube furnace to 950 ℃ at the heating rate of 30 ℃/min under the condition that the argon flow is 100sccm, growing for 30min, naturally cooling to room temperature, and preparing the vertically-grown niobium disulfide nanosheet on a carbon cloth substrate; and placing the carbon cloth substrate with the vertically-grown niobium disulfide nanosheets in a sample box for dry storage to prevent reaction with oxygen.
The present invention will be further explained and analyzed with reference to the accompanying drawings.
The vertically-grown niobium disulfide nanosheets prepared in examples 1-3 have different morphologies, specifically see fig. 2, and therefore the performance of the vertically-grown niobium disulfide nanosheet prepared in example 3 is tested to illustrate the effects of the present invention, specifically see fig. 3. Fig. 1 is an XRD chart of vertically-grown niobium disulfide nanosheets prepared in embodiments 1 to 3 of the present invention, and as shown in fig. 1, the peak positions of the vertically-grown niobium disulfide nanosheets prepared in embodiments 1 to 3 are consistent with those of a standard card, and there are no other miscellaneous peaks except for the peak of the carbon cloth substrate, which indicates that the prepared niobium disulfide nanosheets are high in purity and have no other impurities.
Fig. 2 is an SEM image of the niobium disulfide nanosheets prepared in examples 1-3 of the present invention, (a) is an SEM image of the vertically-grown niobium disulfide nanosheets prepared in example 1, (b) is an SEM image of the niobium disulfide nanosheets prepared in example 2, and (c) is an SEM image of the niobium disulfide nanosheets prepared in example 3. As can be seen from (a), the verticality of the niobium disulfide nanosheet is not high, most of the niobium disulfide nanosheet is similar to a rod shape, no plane two-dimensional shape exists, the size is about 1 mu m, and the specific surface area is greatly increased; as can be seen from (b), the niobium disulfide nanosheets grow vertically, are relatively dense, are petal-shaped, have no planar two-dimensional shape, have the size of about 1 mu m, and have greatly increased specific surface area; from (c), it can be seen that the niobium disulfide nanosheets are large petal-shaped, do not have planar two-dimensional shapes, have a size of about 3 μm, and have a much increased specific surface area but a small number.
FIG. 3 is a diagram of hydrogen production performance of vertically grown niobium disulfide nanosheets prepared in example 2 of the present invention, wherein the carbon cloth substrate is at 10mA/cm 2 The overpotential does not exist, when the niobium disulfide nanosheets vertically grow on the carbon cloth substrate, the overpotential is obviously reduced, the performance is obviously improved, and the performance comparison example of the corresponding embodiment is shown in fig. 3.
In summary, the invention discloses a preparation method of a vertically-grown niobium disulfide nanosheet, which comprises the steps of taking niobium pentachloride and sulfur powder as precursors, and growing for 20-40 min at 850-950 ℃ under the protection of argon gas, wherein the niobium pentachloride is arranged below a carbon cloth substrate, the sulfur powder is arranged at the upstream of the niobium pentachloride, and the distance between the sulfur powder and the center of the carbon cloth substrate is 20-21 cm, so that the vertically-grown niobium disulfide nanosheet can be successfully prepared on the carbon cloth substrate. The vertically grown niobium disulfide nanosheet provided by the invention is coupled with the carbon cloth substrate, the coupling structure is beneficial to effective charge transmission and active site increase, and the prepared niobium disulfide nanosheet has better electrocatalytic activity and stability when being used for electrochemical hydrogen production. Meanwhile, the carbon cloth is cheap in growing substrate, good in controllability of experimental conditions of chemical vapor deposition and easy to introduce into actual industrial production, so that the carbon cloth has wide application prospect in the green chemical industry.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (2)
1. A preparation method of a vertically-grown niobium disulfide nanosheet catalyst for electrochemical hydrogen production is characterized by comprising the following steps: depositing niobium pentachloride and sulfur powder serving as precursors on a carbon cloth substrate by adopting a chemical vapor deposition method to obtain a vertically-grown niobium disulfide nanosheet;
wherein, the niobium pentachloride is arranged below the carbon cloth substrate, the sulfur powder is arranged at the upstream of the niobium pentachloride, and the method specifically comprises the following steps:
placing the reaction boat containing niobium pentachloride in a constant temperature reaction area of a vacuum tube furnace, placing a carbon cloth substrate above the reaction boat, and leaving air vents at two ends of the reaction boat;
the carbon cloth substrate is subjected to pretreatment operation before use, and the pretreatment operation specifically comprises the following steps: ultrasonically cleaning a carbon cloth substrate in absolute ethyl alcohol and deionized water respectively, and then drying;
placing sulfur powder at the upstream position of the airflow of a vacuum tube furnace, wherein the distance between the sulfur powder and the center of a carbon cloth substrate above a reaction boat is 20-21 cm, the mass ratio of niobium pentachloride to the sulfur powder is (1-8): 10, heating the reaction temperature to 850-950 ℃ by a chemical vapor deposition method in an inert atmosphere, and keeping the temperature for 20-40 min; wherein the heating rate is 30 ℃/min, the inert gas flow of the inert atmosphere is 50-200 sccm, and the vertically grown niobium disulfide nanosheet is obtained on the carbon cloth substrate;
the reaction boat and the reaction container are pretreated before use, and the pretreatment method specifically comprises the following steps: the reaction boat and the reaction container are respectively cleaned in absolute ethyl alcohol, isopropanol and acetone by ultrasonic waves, dried and presintered in a vacuum tube furnace, wherein the presintering temperature is 200 ℃, and the presintering time is 30min.
2. The vertically-grown niobium disulfide nanosheet catalyst for electrochemical hydrogen production prepared by the preparation method of the vertically-grown niobium disulfide nanosheet catalyst for electrochemical hydrogen production as claimed in claim 1, wherein the vertically-grown niobium disulfide nanosheet has a size width of 1-3 μm.
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