CN112376066A - MoS constructed by using carbon cloth as substrate2-NiS2Preparation method and application of composite nanosheet electrocatalyst - Google Patents

MoS constructed by using carbon cloth as substrate2-NiS2Preparation method and application of composite nanosheet electrocatalyst Download PDF

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CN112376066A
CN112376066A CN202011089062.6A CN202011089062A CN112376066A CN 112376066 A CN112376066 A CN 112376066A CN 202011089062 A CN202011089062 A CN 202011089062A CN 112376066 A CN112376066 A CN 112376066A
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邱凤仙
许锦超
荣坚
郑云华
朱瑶
张涛
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Jiangsu University
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Abstract

The invention belongs to the technical field of electrochemistry, and relates to a method for constructing MoS by using carbon cloth as a substrate2‑NiS2The preparation method of the composite nanosheet electrocatalyst comprises the following steps: putting the pretreated carbon cloth into a furnace containing NiCl2∙6H2O、NH4F and (NH)2)2Sealing the reaction kettle in CO, carrying out hydrothermal reaction for 4-12 h at the temperature of 80-150 ℃, and drying in vacuum to obtain the product with Ni (OH)2Carbon cloth of nanosheets; anhydrous ethanol solution containing sulfur source and Ni (OH) is grown2Putting the carbon cloth of the nano sheet into a reaction kettle, carrying out hydrothermal reaction for 2-12 h at 100-200 ℃, and carrying out vacuum drying to obtain the NiS2Carbon cloth of nanosheets; the aqueous solution containing the sulfur source and the molybdenum source and the NiS are grown2Putting carbon cloth of nanosheets into a reaction kettleAnd sealing, and reacting for 6-24 hours at 150-240 ℃ to obtain the catalyst. Simple preparation, easy operation, and vertical growth of Ni (OH) by hydrothermal method2The precursor is then converted into NiS by vulcanization2Nanosheet, followed by in situ growth of MoS2The nano-sheet forms a highly porous structure, increases the exposure ratio of active sites and improves the gas diffusion efficiency; the heterogeneous structure is cooperated with the conductive carbon cloth substrate to improve the conductivity of the catalyst.

Description

MoS constructed by using carbon cloth as substrate2-NiS2Preparation method and application of composite nanosheet electrocatalyst
Technical Field
The invention belongs to the technical field of electrochemistry, relates to an electrocatalyst, and particularly relates to a method for constructing MoS by using carbon cloth as a substrate2-NiS2（MoS2/NiS2) A preparation method and application of the composite nanosheet electrocatalyst.
Background
In recent years, problems such as environmental pollution, global warming and energy crisis caused by over-development and utilization of fossil fuels have prompted people to construct a novel clean energy system. Hydrogen as a new energy source is considered as a reasonable alternative energy source to fossil fuels and widely studied because of its zero carbon dioxide emission, high energy density and only water as a combustion product. At present, the main method for industrial hydrogen production still adopts a steam reforming technology using fossil fuel as a raw material, and a large amount of greenhouse gas is generated in the production process, so that the problem of serious environmental pollution is caused. The hydrogen production method (HER) by water electrolysis using clean energy (such as hydropower station) as power has the advantages of low cost, high efficiency and no pollution, and has been widely paid attention to by researchers. The hydrogen evolution catalyst developed at present is mainly applied to strong acid electrolyte, but strong acid solution has strong corrosivity to industrial equipment, so that the cost of industrial application is higher, and therefore, the development of the hydrogen evolution catalyst capable of being applied to alkaline electrolyte has important research value.
To date, the most efficient HER catalysts in both acidic and basic environments are platinum (Pt) -based catalysts, however, the high cost and low shell content greatly limit the use of Pt-based catalysts. The transition metal has the advantages of low cost, high crustal content and the like, and the transition metal-based material design can replace a Pt-based catalyst and has important practical application value. Among them, transition metal disulfides are a class of HER catalysts with broad application prospects. Molybdenum disulfide (MoS)2) As typical two-dimensional flake transition metal disulfidesThe compounds have been widely studied for their advantages of high intrinsic activity, relatively low cost, and excellent stability. However, the results of the study showed that MoS2Since there are few catalytic active sites and poor conductivity, research is focused on improving the conductivity and increasing the number of active sites.
Research shows that the construction of the heterostructure is an effective method for improving the physical and chemical properties of the electrocatalyst. The reasonable construction of the heterogeneous interface is beneficial to adjusting the electron distribution in the material, promoting the electron transfer and improving the chemical adsorption capacity of the electrocatalyst, thereby enhancing the HER activity of the electrocatalyst. Thus, MoS is integrated2、NiS2The heterogeneous structure constructed by the composite nanosheets can effectively improve the conductivity of the catalyst, and the two-dimensional nanosheet structure greatly improves the specific surface area of the material compared with a bulk material, so that more electrocatalytic active sites can be exposed, and the electrocatalyst with high HER activity is prepared. In addition, carbon cloth is widely used as a substrate for in-situ growth of electrocatalytic materials due to its high conductivity and flexibility, and this method of growing materials on carbon cloth not only avoids the use of a binder, but also provides a highly efficient path for electron transfer, electrolyte passage, and gas escape when electrolyzing water, compared to a powder catalyst.
Disclosure of Invention
Based on the problems in the preparation of electrocatalytic hydrogen production materials in the prior art, one object of the invention is to disclose a method for constructing MoS by using carbon cloth as a substrate2/NiS2A preparation method of the composite nanosheet electrocatalyst.
Technical scheme
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano-sheet comprises the steps of firstly growing NiS on the surface of carbon cloth by a three-step hydrothermal method and a solvothermal method2Nanosheets, and further in NiS2Growth of MoS on nanoplates2And (5) nanosheet to obtain a composite nanosheet structure.
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nanosheet electrocatalyst comprises the following steps:
a) after pretreatmentIs put into a carbon cloth containing NiCl2∙6H2O、NH4F and (NH)2)2Sealing in a polytetrafluoroethylene reaction kettle containing 35 mL of CO aqueous solution, reacting at 80-150 ℃ for 4-12 h, preferably 110 ℃ and 8 h, naturally cooling to room temperature, taking out, sequentially washing with deionized water and ethanol, and vacuum drying at 60 ℃ to obtain the growth product of Ni (OH)2Carbon cloth of nanosheets;
b) 25 mL of an anhydrous ethanol solution containing a sulfur source and Ni (OH) grown as described above2Putting the carbon cloth of the nanosheets into a polytetrafluoroethylene reaction kettle, sealing, reacting for 2-12 h at 100-200 ℃, preferably 150 ℃ and 6 h, naturally cooling to room temperature, taking out, sequentially washing with deionized water and ethanol, and drying at 60 ℃ in vacuum to obtain the NiS grown2Carbon cloth of nanosheets;
c) 40 mL of an aqueous solution containing a sulfur source and a molybdenum source and NiS grown as described above2Putting the carbon cloth of the nanosheets into a polytetrafluoroethylene reaction kettle, sealing, reacting for 6-24 h at 150-240 ℃, preferably 200 ℃ and 12 h, naturally cooling, taking out, sequentially washing with deionized water and ethanol, and drying at 60 ℃ in vacuum to obtain the MoS grown2/NiS2Carbon cloth of composite nano-sheet.
In a preferred embodiment of the invention, the NiCl in step a) is2∙6H2The concentration of O is 0.03-0.20 mol/L, preferably 0.06 mol/L; the NH4The concentration of F is 0.03-0.30 mol/L, preferably 0.15 mol/L; said (NH)2)2The concentration of CO is 0.06-0.45 mol/L, preferably 0.21 mol/L.
In a preferred embodiment of the invention, the carbon cloth pretreated in the step a) is cut into blocks, immersed in 1-6 mol/L nitric acid solution, heated to 40-90 ℃, preferably 70 ℃, continuously stirred for 2-8 h, preferably 5 h, cooled, taken out and sequentially cleaned with deionized water and ethanol for 15min by ultrasonic waves; wherein the carbon cloth is cut into blocks with the size of 20 mm multiplied by 20 mm, and the nitric acid solution is 3 mol/L.
In the preferred embodiment of the invention, the sulfur source in step b) is sodium sulfide (Na)2S), thiourea (N)2H4CS), thioacetamide (CH)3CSNH2) Or L-cysteine (C)3H7NO2S) at a concentration of 1-10 mg/mL, preferably CH3CSNH2At a concentration of 4 mg/mL.
In a preferred embodiment of the present invention, the sulfur source in step c) is thiourea (N)2H4CS), thioacetamide (CH)3CSNH2) Or L-cysteine (C)3H7NO2S) at a concentration of 1 to 10 mg/mL, preferably N2H4CS, concentration 4 mg/mL; the molybdenum source is (NH)4)6Mo7O24·4H2O、MoCl5、Na2MoO4·2H2O、(NH4)2MoS4、H2MoO4Any one of the above (1) at a concentration of 0.5 to 5 mg/mL, preferably (NH)4)6Mo7O24·4H2O, concentration 2 mg/mL.
Another purpose of the invention is to disclose the prepared MoS in situ grown by taking the carbon cloth as a substrate2/NiS2The composite nanometer electrocatalyst is used in electrolyzing water to separate out hydrogen.
Laboratory test experiment for electro-catalytic hydrogen evolution performance
The prepared MoS grows on2/NiS2The carbon cloth finished catalyst of the composite nanosheet is used as a working electrode, 1.0 mol/L KOH solution is used as electrolyte, a three-electrode system is selected to measure the electro-catalytic hydrogen evolution performance of the catalyst, Hg/HgO or Ag/AgCl is selected as a reference electrode of the three-electrode system, and a carbon rod or a platinum wire is selected as a counter electrode.
The invention has the characteristics that:
(1) the carbon cloth is selected as the substrate, so that the stability is strong, the flexibility is high, the price is low, and the source is rich;
(2) construction of MoS2/NiS2The method of the composite nanosheet forms a large number of heterogeneous structures in the material, which is beneficial to improving the conductivity of the material and improving the chemical adsorption capacity of the material, thereby improving the electrocatalytic hydrogen evolution activity;
（3）MoS2/NiS2the composite nanosheets vertically grow on the carbon cloth substrate to form a developed porous structure, the specific surface area of the material is increased, more catalytic active sites are exposed, gas diffusion is facilitated, and the catalytic efficiency is improved.
Advantageous effects
The invention discloses a method for constructing MoS based on carbon cloth as a substrate2/NiS2The preparation method of the composite nanosheet electrocatalytic hydrogen production material has the advantages of simple preparation process, easy operation and relatively mild reaction conditions; the prepared material takes carbon cloth as a substrate, and vertically grows Ni (OH) by a hydrothermal method2The precursor is then converted into NiS by vulcanization2Nanosheet, followed by in situ growth of MoS2The nanosheets form a highly porous structure, so that the exposure ratio of active sites is increased, and the gas diffusion efficiency is improved; on the other hand, the conductivity of the material is improved by the heterostructure in the material in cooperation with the conductive carbon cloth substrate, and the obtained catalyst shows high activity and high stability.
Drawings
FIG. 1 MoS prepared in example 42/NiS2SEM of composite nano-sheet;
FIG. 2 MoS prepared in example 42/NiS2TEM of composite nanoplatelets.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
In-situ growth MoS with carbon cloth as substrate2/NiS2Composite nano electrocatalysisThe preparation method of the reagent comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (1 mol/L), heated to 40 ℃ and continuously stirred for 2 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.03 mol/L）、NH4F (0.03 mol/L) and (NH)2)2CO (0.06 mol/L) in a Teflon reaction kettle containing 35 mL of aqueous solution, sealing and reacting at 80 ℃ for 4 h. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of Na-containing solution2S (1 mg/mL) in absolute ethanol and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 2 h at 100 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain NiS2Carbon cloth of nano-sheet.
d) 40 mL of N-containing solution2H4CS (1 mg/mL) and (NH)4)6Mo7O24·4H2Aqueous solution of O (0.5 mg/mL) and grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 6 h at 150 ℃. After natural cooling, the material was taken out, washed with deionized water and ethanol three times in order, and then vacuum-dried at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
A three-electrode system is selected to measure the electrochemical performance, a 1 mol/L KOH solution is used as an electrolyte, the prepared carbon cloth finished catalyst is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and an LSV polarization curve is tested. When the current density reaches 10 mA/cm-2When the prepared electrocatalyst requires an overpotential of196 mV。
Example 2
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano electro-catalyst comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (2 mol/L), heated to 50 ℃ and continuously stirred for 3 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.06 mol/L）、NH4F (0.09 mol/L) and (NH)2)2CO (0.12 mol/L) was reacted at 90 ℃ for 5 hours in a Teflon reaction vessel containing 35 mL of an aqueous solution, which was sealed. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of N-containing solution2H4CS (2 mg/mL) in absolute ethanol and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 3 h at 120 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain NiS2Carbon cloth of nano-sheet.
d) 40 mL of a solution containing C3H7NO2S (2 mg/mL) and H2MoO4(1 mg/mL) of an aqueous solution and the grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 8 h at 160 ℃. After natural cooling, the material was taken out, washed with deionized water and ethanol three times in order, and then vacuum-dried at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
Selecting a three-electrode system to measure the electrochemical performance, taking 1 mol/L KOH solution as electrolyte, taking the prepared carbon cloth finished catalyst as a working electrode, and taking Hg/HgOThe LSV polarization curve was tested with a reference electrode and a platinum wire as the counter electrode. When the current density reaches 10 mA/cm-2The prepared electrocatalyst required an overpotential of 188 mV.
Example 3
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano electro-catalyst comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (3 mol/L), heated to 60 ℃ and continuously stirred for 4 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.09 mol/L）、NH4F (0.12 mol/L) and (NH)2)2CO (0.18 mol/L) was reacted at 100 ℃ for 6 hours in a Teflon reaction vessel containing 35 mL of an aqueous solution, which was sealed. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of a solution containing C3H7NO2S (4 mg/mL) absolute ethanol solution and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 4 h at 140 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain NiS2Carbon cloth of nano-sheet.
d) 40 mL of CH-containing solution3CSNH2(3 mg/mL) and Na2MoO4·2H2Aqueous solution of O (1.5 mg/mL) and grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 10 h at 180 ℃. After natural cooling, the material was taken out, washed with deionized water and ethanol three times in order, and then vacuum-dried at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
A three-electrode system is selected to measure the electrochemical performance, a 1 mol/L KOH solution is used as an electrolyte, the prepared carbon cloth finished catalyst is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and an LSV polarization curve is tested. When the current density reaches 10 mA/cm-2The prepared electrocatalyst required an overpotential of 177 mV.
Example 4
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano electro-catalyst comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (3 mol/L), heated to 70 ℃ and continuously stirred for 5 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.06 mol/L）、NH4F (0.15 mol/L) and (NH)2)2CO (0.21 mol/L) was reacted at 110 ℃ for 8 hours in a Teflon reaction vessel containing 35 mL of an aqueous solution, which was sealed. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of CH-containing solution3CSNH2(4 mg/mL) of an anhydrous ethanol solution and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 6 h at 150 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain NiS2Carbon cloth of nano-sheet.
d) 40 mL of N-containing solution2H4CS (4 mg/mL) and (NH)4)6Mo7O24·4H2Aqueous solution of O (2 mg/mL) and grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 12 h at 200 ℃. FromAfter cooling, the material was taken out, washed three times with deionized water and ethanol in sequence, and then dried under vacuum at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
A three-electrode system is selected to measure the electrochemical performance, a 1 mol/L KOH solution is used as an electrolyte, the prepared carbon cloth finished catalyst is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and an LSV polarization curve is tested. When the current density reaches 10 mA/cm-2The prepared electrocatalyst required an overpotential of 80 mV.
Example 5
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano electro-catalyst comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (5 mol/L), heated to 80 ℃ and continuously stirred for 6 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.15 mol/L）、NH4F (0.21 mol/L) and (NH)2)2CO (0.30 mol/L) in a Teflon reaction kettle containing 35 mL of aqueous solution, sealing and reacting at 120 ℃ for 10 h. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of CH-containing solution3CSNH2(6 mg/mL) of an anhydrous ethanol solution and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 8 h at 180 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain NiS2Carbon cloth of nano-sheet.
d) 40 mL of N-containing solution2H4CS (6 mg/mL) and (NH)4)6Mo7O24·4H2Aqueous solution of O (3 mg/mL) and grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 18 h at 220 ℃. After natural cooling, the material was taken out, washed with deionized water and ethanol three times in order, and then vacuum-dried at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
A three-electrode system is selected to measure the electrochemical performance, a 1 mol/L KOH solution is used as an electrolyte, the prepared carbon cloth finished catalyst is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and an LSV polarization curve is tested. When the current density reaches 10 mA/cm-2The prepared electrocatalyst required an overpotential of 158 mV.
Example 6
In-situ growth MoS with carbon cloth as substrate2/NiS2The preparation method of the composite nano electro-catalyst comprises the following steps:
a) the carbon cloth was cut into 20X 20 mm pieces, then immersed in 50 mL of a nitric acid solution (6 mol/L), heated to 90 ℃ and continuously stirred for 8 hours, after cooling, the carbon cloth was taken out and ultrasonically cleaned with deionized water and ethanol in this order for 15 minutes.
b) Putting the carbon cloth pretreated in the step a) into a furnace containing NiCl2∙6H2O（0.20 mol/L）、NH4F (0.30 mol/L) and (NH)2)2CO (0.45 mol/L) in a Teflon reaction kettle containing 35 mL of aqueous solution, sealing and reacting at 150 ℃ for 12 h. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtain Ni (OH) grown2Carbon cloth of nano-sheet.
c) 25 mL of CH-containing solution3CSNH2(10 mg/mL) of an anhydrous ethanol solution and grown Ni (OH) synthesized in step b)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 12 h at 200 ℃. Naturally cooling to room temperature, taking out the material, sequentially washing with deionized water and ethanol for three times, and vacuum drying at 60 deg.C to obtainNiS grows2Carbon cloth of nano-sheet.
d) 40 mL of CH-containing solution3CSNH2(10 mg/mL) and Na2MoO4·2H2Aqueous solution of O (5 mg/mL) and grown NiS synthesized in step c)2Putting the carbon cloth of the nano-sheets into a polytetrafluoroethylene reaction kettle, sealing, and reacting for 24 h at 240 ℃. After natural cooling, the material was taken out, washed with deionized water and ethanol three times in order, and then vacuum-dried at 60 ℃ to obtain grown MoS2/NiS2Carbon cloth of composite nano-sheet.
A three-electrode system is selected to measure the electrochemical performance, a 1 mol/L KOH solution is used as an electrolyte, the prepared carbon cloth finished catalyst is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and an LSV polarization curve is tested. When the current density reaches 10 mA/cm-2The prepared electrocatalyst required an overpotential of 167 mV.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (10)

1.一种以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于，包括如下步骤：1. a kind of preparation method of MoS 2 /NiS 2 composite nano-sheet electrocatalyst with carbon cloth as substrate in-situ growth, is characterized in that, comprises the steps: a）将预处理后的碳布放入含有NiCl2∙6H2O、NH4F和(NH2)2CO的35 mL水溶液的聚四氟乙烯反应釜中，密封，80～150℃反应4～12 h，自然冷却至室温，取出，依次用去离子水和乙醇洗净，60℃真空干燥得到生长了Ni(OH)2纳米片的碳布；a) Put the pretreated carbon cloth into a polytetrafluoroethylene reactor containing a 35 mL aqueous solution of NiCl 2 ∙6H 2 O, NH 4 F and (NH 2 ) 2 CO, seal it, and react at 80-150 °C for 4 ~12 h, naturally cooled to room temperature, taken out, washed with deionized water and ethanol in turn, and vacuum dried at 60 °C to obtain a carbon cloth with Ni(OH) 2 nanosheets grown; b）将25 mL的含硫源的无水乙醇溶液和上述生长了Ni(OH)2纳米片的碳布一起放入聚四氟乙烯反应釜中，密封，100～200℃反应2～12 h，自然冷却至室温后，取出，依次用去离子水和乙醇洗净，60℃真空干燥得到生长了NiS2纳米片的碳布；b) Put 25 mL of anhydrous ethanol solution containing sulfur source and the above carbon cloth on which Ni(OH) 2 nanosheets are grown into a PTFE reactor, seal it, and react at 100-200 °C for 2-12 h , cooled to room temperature naturally, taken out, washed with deionized water and ethanol in turn, and vacuum dried at 60 °C to obtain a carbon cloth with NiS 2 nanosheets grown; c）将40 mL的含硫源和钼源的水溶液和上述生长了NiS2纳米片的碳布一起放入聚四氟乙烯反应釜中，密封，150～240℃反应6～24 h，自然冷却后，取出，依次用去离子水和乙醇洗净，60℃真空干燥得到生长了MoS2/NiS2复合纳米片的碳布。c) Put 40 mL of the aqueous solution containing sulfur source and molybdenum source together with the above carbon cloth on which NiS 2 nanosheets have grown into a PTFE reactor, seal, react at 150-240 °C for 6-24 h, and cool naturally After that, it was taken out, washed with deionized water and ethanol in turn, and vacuum dried at 60 °C to obtain a carbon cloth with MoS 2 /NiS 2 composite nanosheets grown. 2.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤a）中所述NiCl2∙6H2O其浓度为0.03～0.20 mol/L，所述NH4F其浓度为0.03～0.30 mol/L，所述(NH2)2CO其浓度为0.06～0.45 mol/L。2. The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, wherein the concentration of NiCl 2 ∙6H 2 O in step a) is 0.03 ～0.20 mol/L, the concentration of the NH 4 F is 0.03-0.30 mol/L, and the concentration of the (NH 2 ) 2 CO is 0.06-0.45 mol/L. 3.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤a）中所述NiCl2∙6H2O其浓度为0.06 mol/L，所述NH4F其浓度为0.15mol/L，所述(NH2)2CO其浓度为0.21 mol/L。3. The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, wherein the concentration of NiCl 2 ∙6H 2 O in step a) is 0.06 mol/L, the concentration of the NH 4 F is 0.15 mol/L, and the concentration of the (NH 2 ) 2 CO is 0.21 mol/L. 4.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤a）中所述将预处理后的碳布放入含有NiCl2∙6H2O、NH4F和(NH2)2CO的35mL水溶液的聚四氟乙烯反应釜中，密封，110℃反应8 h。4. The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, characterized in that: in step a), the pretreated carbon cloth is placed in an electrocatalyst containing The 35mL aqueous solution of NiCl 2 ∙6H 2 O, NH 4 F and (NH 2 ) 2 CO was placed in a polytetrafluoroethylene reactor, sealed, and reacted at 110 °C for 8 h. 5.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤b）中所述将25 mL的含硫源的无水乙醇溶液和上述生长了Ni(OH)2纳米片的碳布一起放入聚四氟乙烯反应釜中，密封，150℃反应6 h。5. The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, characterized in that: described in step b), adding 25 mL of anhydrous sulfur-containing source The ethanol solution and the carbon cloth on which Ni(OH) 2 nanosheets were grown were put into a polytetrafluoroethylene reactor, sealed, and reacted at 150 °C for 6 h. 6.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤b）中所述硫源为硫化钠Na2S、硫脲N2H4CS、硫代乙酰胺CH3CSNH2或L-半胱氨酸C3H7NO2S中的任一种，浓度1～10 mg/mL，优选CH3CSNH2，浓度4 mg/mL。6. The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, wherein the sulfur source in step b) is sodium sulfide Na 2 S, sulfur Any of urea N 2 H 4 CS, thioacetamide CH 3 CSNH 2 or L-cysteine C 3 H 7 NO 2 S, concentration 1-10 mg/mL, preferably CH 3 CSNH 2 , concentration 4 mg/mL. 7.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤c）中所述将40 mL的含硫源和钼源的水溶液和上述生长了NiS2纳米片的碳布一起放入聚四氟乙烯反应釜中，密封，200℃反应12 h。7 . The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst using carbon cloth as a substrate according to claim 1, characterized in that: in step c), 40 mL of sulfur-containing source and molybdenum source are added The aqueous solution and the above-mentioned carbon cloth on which NiS 2 nanosheets were grown were put into a polytetrafluoroethylene reactor, sealed, and reacted at 200 °C for 12 h. 8.根据权利要求1所述以碳布为基底原位生长MoS2/NiS2复合纳米片电催化剂的制备方法，其特征在于：步骤c）中所述硫源为硫脲N2H4CS、硫代乙酰胺CH3CSNH2或L-半胱氨酸C3H7NO2S中的任一种，浓度1～10 mg/mL，优选N2H4CS，浓度4 mg/mL；所述钼源为(NH4)6Mo7O24·4H2O、MoCl5、Na2MoO4·2H2O、(NH4)2MoS4、H2MoO4中的任一种，浓度0.5～5 mg/mL，优选(NH4)6Mo7O24·4H2O，浓度为2 mg/mL。8 . The preparation method for in-situ growth of MoS 2 /NiS 2 composite nanosheet electrocatalyst with carbon cloth as substrate according to claim 1 , wherein the sulfur source in step c) is thiourea N 2 H 4 CS , any one of thioacetamide CH 3 CSNH 2 or L-cysteine C 3 H 7 NO 2 S, with a concentration of 1 to 10 mg/mL, preferably N 2 H 4 CS, with a concentration of 4 mg/mL; The molybdenum source is any one of (NH 4 ) 6 Mo 7 O 24 .4H 2 O, MoCl 5 , Na 2 MoO 4 .2H 2 O, (NH 4 ) 2 MoS 4 , and H 2 MoO 4 , and the concentration 0.5-5 mg/mL, preferably (NH 4 ) 6 Mo 7 O 24 ·4H 2 O, with a concentration of 2 mg/mL. 9.根据上述权利要求1-8任一所述方法制得的以碳布为基底原位生长MoS2/NiS2复合纳米电催化剂。9 . The MoS 2 /NiS 2 composite nano-electrocatalyst is grown in situ with carbon cloth as a substrate prepared according to any one of the above claims 1-8. 10.一种权利要求9所述电催化剂的应用，其特征在于：将其应用于电解水析氢。10. An application of the electrocatalyst according to claim 9, characterized in that: it is applied to the electrolysis of water for hydrogen evolution.
CN202011089062.6A 2020-10-13 2020-10-13 MoS constructed by using carbon cloth as substrate2-NiS2Preparation method and application of composite nanosheet electrocatalyst Pending CN112376066A (en)

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