CN111514911A - Carbon-doped WP nanosheet electrocatalyst with mesoporous structure and preparation method thereof - Google Patents
Carbon-doped WP nanosheet electrocatalyst with mesoporous structure and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 26
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
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- 238000004140 cleaning Methods 0.000 claims abstract description 3
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- 238000001035 drying Methods 0.000 claims description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention provides a preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, which comprises the following steps of: (1) preparation of the sheet WO3·2H2O powder: (2) WO3Preparation of amine substance hybrid precursor powder: get WO3·2H2Adding the O block powder and the amine substance into a polytetrafluoroethylene reaction kettle, reacting for 24-72h at the temperature of 100 ℃ and 200 ℃ to obtain white precipitate, centrifugally cleaning for several times by using ethanol, and then carrying out centrifugal cleaningDrying to obtain WO3White solid powder of amine substance hybrid precursor; (3) preparation of WP @ C: sodium hypophosphite is used as a phosphorus source, and a double-temperature-control vacuum atmosphere tube furnace is used for firstly leading WO3Decomposition of amine hybrid precursor into WOx@ C complex, then WOxThe @ C complex is phosphitylated and reduced to a sheet-like WP @ C electrocatalytic material. The carbon-doped WP nanosheet electrocatalytic material prepared by the method has high specific surface area and electrical conductivity.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis and hydrogen evolution electrode materials, and particularly relates to a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, and a preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure.
Background
The method for preparing the renewable clean energy hydrogen by electrocatalytic decomposition of water is a promising method because of the advantages of simple process, low cost, environmental protection, no pollution and the like. At present, the research focus in the field of hydrogen production by water electrolysis is how to develop a stable and efficient non-noble metal catalyst which can replace noble metals such as Pt.
Among them, two-dimensional transition metal semiconductor materials have been widely studied due to their wide sources and excellent properties, but these two-dimensional layered materials exhibit limited intrinsic electrocatalytic activity due to poor electrical conductivity and slow charge transfer kinetics. There are many strategies available today to enhance the electrical conductivity of materials, such as synthesizing metallic strong semiconductor materials or using highly conductive matrix materials (e.g., carbon materials or noble metals) that can significantly enhance the electrical conductivity of materials to enhance the electrocatalytic hydrogen evolution performance. Carbon materials have been receiving attention in various fields (such as energy, device, and catalyst) because of their excellent conductivity and stability, and particularly, have been widely used in the electrocatalytic direction, such as graphene, amorphous carbon materials, carbon nanotubes, and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, and solves the problem that the existing WP nanosheet is not excellent in conductivity and electrocatalytic hydrogen evolution performance.
The second purpose of the invention is to provide a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, which is prepared by the method.
The first purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure comprises the following steps:
(1) preparation of the sheet WO3·2H2O powder: mixing Na2WO4·2H2Adding the O solution into the HCl solution for reaction, centrifuging the obtained light yellow suspension after the reaction is finished, washing the light yellow suspension for a plurality of times by using deionized water, and finally drying the obtained light yellow substance by using a freeze dryer to obtain the lamella WO3·2H2O block powder;
(2)WO3preparation of amine substance hybrid precursor powder: get WO3·2H2Adding the O block powder and the amine substance into a polytetrafluoroethylene reaction kettle, reacting for 24-72h at the temperature of 100-200 ℃ to obtain white precipitate, centrifugally cleaning the white precipitate for a plurality of times by using ethanol, and drying the white precipitate to obtain WO3White solid powder of amine substance hybrid precursor;
(3) preparation of WP @ C: sodium hypophosphite is used as a phosphorus source, and a double-temperature-control vacuum atmosphere tube furnace is used for firstly leading WO3Decomposition of white solid powder of amine substance hybrid precursor into WOx@ C complex, then WOxThe @ C complex is phosphitylated and reduced to a sheet-like WP @ C electrocatalytic material.
The invention adopts a solvothermal method, a thermal decomposition method and an in-situ phosphorization reduction method, and uses a WO 3/amine substance hybrid precursor to prepare the carbon-doped WP nanosheet with the mesoporous structure. .
The preparation method of the invention can be further improved as follows:
the concentration of the sodium tungstate solution in the step (1): 1-3mol/L, hydrochloric acid solution concentration: 2-5 mol/L.
WO in step (2)3·2H2Mass of O powder: 0.1-2g, volume of amine substance:4-80mL。
in the step (2), the amine substance is one of n-propylamine, n-butylamine and n-octylamine.
The mass of the sodium hypophosphite in the step (2) is 1-3 g.
The step (2) is specifically operated as follows: placing sodium hypophosphite in a quartz boat in the central heating zone at the upstream of the two-temperature zone tube furnace, and placing WO3Putting white solid powder of the amine substance hybrid precursor on another quartz boat positioned in a central heating zone at the downstream of the double-temperature zone tubular furnace; introducing argon to remove air, heating the downstream central heating zone to 600 ℃ at the temperature rise rate of 1-5 ℃/min under atmospheric pressure for 0.5-1.5h, then heating to 850 ℃ at the temperature rise rate of 650-10 ℃/min for 1-3h, simultaneously heating the upstream central heating zone to 350 ℃ at the temperature of 250-5 ℃ and preserving heat for 1-3 h.
Further, the operation of introducing argon to remove air is as follows: before the heating process, vacuumizing and ventilating the quartz tube for 2 times under Ar atmosphere to obtain inert atmosphere; and in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 10 s.c.c.m.
The second purpose of the invention is realized by the following technical scheme:
a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure is prepared by the preparation method, and the material has a large specific surface area and excellent electrocatalytic hydrogen evolution performance. The current density in the acid electrolyte was 10mA cm-2The overpotential is 190mV, the Tafel slope is 108mV dec-1。
(2) The preparation method is novel, low in cost and simple to operate, provides valuable insight for improving the conductivity and the specific surface area of the carbon material modified material by using the carbon material so as to improve the performance, and contributes to promoting the development of the organic-inorganic hybrid catalyst material in the field of hydrogen evolution by electrocatalysis.
Drawings
Fig. 1 is an XRD spectrum of the WP @ C nanosheet electro-catalytic hydrogen evolution electrode material obtained in example 1 of the present invention.
Fig. 2 is an SEM image of the WP @ C nanosheet electrocatalytic hydrogen evolution electrode material obtained in example 1 of the present invention.
Fig. 3 and 4 are BET diagrams of the WP @ C nanosheet electrocatalytic hydrogen evolution electrode material obtained in example 1 of the present invention.
Fig. 5 is an LSV curve of the WP @ C nanosheet electrocatalytic hydrogen evolution electrode material obtained in example 1 of the present invention.
Fig. 6 is a Tafel plot of the WP @ C nanosheet electrocatalytic hydrogen evolution electrode material obtained in example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with specific examples to better understand and implement the technical solutions of the present invention for those skilled in the art.
Example 1
A preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure comprises the following steps:
(1) preparation of the sheet WO3·2H2O powder: 10mL of sodium tungstate Na2WO4·2H2Solution O (1.0M) was added to 90mL of HCl solution (3.0M) and magnetically stirred in an ice-water bath for 30min, and an immediate formation of a white precipitate was observed, with the solution becoming yellow as the reaction proceeded. Centrifuging the obtained light yellow suspension, washing with deionized water for several times until the pH is approximately equal to 7, and drying the obtained light yellow substance with a freeze dryer to obtain a lamellar solid substance, namely, the lamellar WO3·2H2O block powder.
(2)WO3Preparation of n-propylamine hybrid precursor powder: 0.4g of WO lumps are weighed out3·2H2Adding O into a 50mL polytetrafluoroethylene reaction kettle liner, weighing 16mL of n-propylamine by using a dried measuring cylinder, pouring into the reaction kettle, putting the reaction kettle into a 160 ℃ oven for reaction for 48 hours, taking out, and naturally cooling to room temperature. After cooling, collecting white precipitate in the sample, and separating with anhydrous ethanolCentrifuging at 7000rpm for 5min in a centrifuge, drying in a 60 deg.C oven for 48 hr, and collecting white precipitate3N-propylamine hybrid precursor.
(3) Preparation of WP @ C: the samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. Drying the obtained WO3Putting the white solid powder of the n-propylamine precursor into a central heating zone at the downstream of the quartz tube. Vacuumizing the quartz tube in Ar atmosphere for 2 times to obtain inert atmosphere, heating the downstream of the tube furnace to 500 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 30min to obtain WOxa/C complex. The sample was then heated to 700 ℃ at a ramp rate of 2 ℃/min and held at 700 ℃ for 2h while weighing 1.0g NaH2PO2Heating up to 300 ℃ at the temperature rising rate of 5 ℃/min at the upstream of the tube furnace, preserving heat for 2h, and naturally cooling after the reaction is completed. The gas circuit system in the temperature rising stage is aerated with argon flow of 100s.c.c.m, and the flow is switched to 10s.c.c.m in the reaction stage. And taking out the sintered WP @ C sample after the temperature of the tube furnace is reduced to the room temperature.
Example 2
A preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure comprises the following steps:
(1) preparation of the sheet WO3·2H2O powder: 10mL of sodium tungstate Na2WO4·2H2Solution O (1.0M) was added to 90mL of HCl solution (3.0M) and magnetically stirred in an ice-water bath for 30min, and an immediate formation of a white precipitate was observed, with the solution becoming yellow as the reaction proceeded. Centrifuging the obtained light yellow suspension, washing with deionized water for several times until the pH is approximately equal to 7, and drying the obtained light yellow substance with a freeze dryer to obtain a lamellar solid substance, namely, the lamellar WO3·2H2O block powder.
(2)WO3Preparation of n-butylamine hybrid precursor powder: 0.8g of block WO is weighed3·2H2Adding O into a 50mL polytetrafluoroethylene reaction kettle liner, weighing 32mL n-butylamine by using a dried measuring cylinder, pouring into the reaction kettle, putting the reaction kettle into an oven at 180 ℃ for reaction for 48 hours, taking out, and naturally cooling to room temperature.Cooling, collecting white precipitate, centrifuging with anhydrous ethanol at 7000rpm for 5min in a centrifuge, drying in 60 deg.C oven for 48 hr, and collecting white precipitate3N-butylamine hybrid precursor.
(3) Preparation of WP @ C: the samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. Drying the obtained WO3Putting the white solid powder of the n-butylamine precursor into a central heating zone at the downstream of the quartz tube. Vacuumizing the quartz tube in Ar atmosphere for 2 times to obtain inert atmosphere, heating the downstream of the tube furnace to 550 ℃ at the heating rate of 1 ℃/min, and preserving the heat for 30min to obtain WOxa/C complex. The sample was then heated to 700 ℃ at a ramp rate of 2 ℃/min and held at 700 ℃ for 2h while weighing 1.0g NaH2PO2Heating up to 300 ℃ at the temperature rising rate of 5 ℃/min at the upstream of the tube furnace, preserving heat for 2h, and naturally cooling after the reaction is completed. The gas circuit system in the temperature rising stage is aerated with argon flow of 100s.c.c.m, and the flow is switched to 10s.c.c.m in the reaction stage. And taking out the sintered WP @ C sample after the temperature of the tube furnace is reduced to the room temperature.
Example 3
A preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure comprises the following steps:
(1) preparation of the sheet WO3·2H2O powder: 10mL of sodium tungstate Na2WO4·2H2Solution O (1.0M) was added to 90mL of HCl solution (3.0M) and magnetically stirred in an ice-water bath for 30min, and an immediate formation of a white precipitate was observed, with the solution becoming yellow as the reaction proceeded. Centrifuging the obtained light yellow suspension, washing with deionized water for several times until the pH is approximately equal to 7, and drying the obtained light yellow substance with a freeze dryer to obtain a lamellar solid substance, namely, the lamellar WO3·2H2O block powder.
(2)WO3Preparation of n-octylamine hybrid precursor powder: 0.4g of WO lumps are weighed out3·2H2Adding O into a 50mL polytetrafluoroethylene reaction kettle liner, measuring 16mL of n-octylamine by using a dried measuring cylinder, pouring into the reaction kettle, and placing the reaction kettleAnd (4) reacting for 72 hours in an oven at 160 ℃, taking out and naturally cooling to room temperature. Cooling, collecting white precipitate, centrifuging with anhydrous ethanol at 7000rpm for 5min in a centrifuge, drying in 60 deg.C oven for 48 hr, and collecting white precipitate3A n-octylamine hybrid precursor.
(3) Preparation of WP @ C: the samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. Drying the obtained WO3And/or putting the white solid powder of the n-octylamine precursor into a central heating zone at the downstream of the quartz tube. Vacuumizing the quartz tube in Ar atmosphere for 2 times to obtain inert atmosphere, heating the downstream of the tube furnace to 500 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 30min to obtain WOxa/C complex. The sample was then heated to 750 ℃ at a ramp rate of 2 ℃/min and held at 750 ℃ for 2h while weighing 1.0g NaH2PO2Heating up to 300 ℃ at the temperature rising rate of 5 ℃/min at the upstream of the tube furnace, preserving heat for 2h, and naturally cooling after the reaction is completed. The gas circuit system in the temperature rising stage is aerated with argon flow of 100s.c.c.m, and the flow is switched to 10s.c.c.m in the reaction stage. And taking out the sintered WP @ C sample after the temperature of the tube furnace is reduced to the room temperature.
And (3) electrochemical performance testing: glassy carbon electrode decorated with catalyst samples as working electrode: 5mg of WP @ C sample powder was weighed out and dispersed in a mixed solution containing 1mL of ethanol/water (v/v ═ 500/500) and 20. mu.L of Nafion, and a uniform ink was formed by sonication for 30 min. Then loading 5 mu L of catalyst electrolyte on a pretreated glassy carbon electrode with the diameter of 3mm, and naturally drying to obtain a working electrode, wherein the graphite rod is used as an auxiliary electrode, and the calomel electrode is used as a reference electrode. 0.5mol/L H saturated with nitrogen at room temperature2SO4And carrying out electrocatalytic hydrogen evolution performance test in the electrolyte.
As shown in fig. 1, an XRD pattern of the electrode material prepared in example 1. The characteristic diffraction peaks of WP @ C appeared at 21.1 °, 28.7 °, 31.1 °, 42.9 °, 44.6 ° and 46.5 ° for 2 θ, which perfectly matched the orthorhombic phase of WP standard card (JCPDS No.29-1364), indicating that the prepared samples were carbon-doped tungsten phosphide samples.
As shown in fig. 2, is an SEM image of the electrode material prepared in example 1. The figure shows that the nano-particles are in irregular nano-sheet shapes, the lamellar structure is clear and visible, the aggregation phenomenon is avoided, and the specific surface area is large.
As shown in fig. 3 and 4, BET graphs of the electrode materials prepared in example 1 are shown. From the figure it can be seen that the sheet like WP @ C nanomaterial has a thickness of 5.59m2·g-1Is a porous material, and the void size is concentrated within 6 nm.
As shown in fig. 5 and 6, LSV curves and Tafel plots for the electrode material prepared in example 1. The graph shows that the WP @ C material has better electro-catalytic hydrogen evolution performance in acidity, and the current density is 10 mA-cm-2The overpotential is 190mV, and the corresponding Tafel slope is 108mV dec-1。
The above embodiments illustrate various embodiments of the present invention in detail, but the embodiments of the present invention are not limited thereto, and those skilled in the art can achieve the objectives of the present invention based on the disclosure of the present invention, and any modifications and variations based on the concept of the present invention fall within the scope of the present invention, which is defined by the claims.
Claims (8)
1. A preparation method of a carbon-doped WP nanosheet electrocatalyst with a mesoporous structure is characterized by comprising the following steps of:
(1) preparation of the sheet WO3·2H2O powder: mixing Na2WO4·2H2Adding the O solution into the HCl solution for reaction, centrifuging the obtained light yellow suspension after the reaction is finished, washing the light yellow suspension for a plurality of times by using deionized water, and finally drying the obtained light yellow substance by using a freeze dryer to obtain the lamella WO3·2H2O block powder;
(2)WO3preparation of amine substance hybrid precursor powder: get WO3·2H2Adding the O block powder and the amine substance into a polytetrafluoroethylene reaction kettle, reacting for 24-72h at the temperature of 100-200 ℃ to obtain white precipitate, centrifugally cleaning the white precipitate for a plurality of times by using ethanol, and drying the white precipitate to obtain WO3White solid powder of amine substance hybrid precursor;
(3) preparation of WP @ C: sodium hypophosphite is used as a phosphorus source, and a double-temperature-control vacuum atmosphere tube furnace is used for firstly leading WO3Decomposition of white solid powder of amine substance hybrid precursor into WOx@ C complex, then WOxThe @ C complex is phosphitylated and reduced to a sheet-like WP @ C electrocatalytic material.
2. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to claim 1, wherein the concentration of the sodium tungstate solution in step (1) is as follows: 1-3mol/L, hydrochloric acid solution concentration: 2-5 mol/L.
3. The preparation method of the carbon-doped WP nanosheet electrocatalyst with a mesoporous structure according to claim 1, wherein WO is applied to step (2)3·2H2Mass of O powder: 0.1-2g, volume of amine substance: 4-80 mL.
4. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to any one of claims 1 to 3, wherein in the step (2), the amine substance is one of n-propylamine, n-butylamine and n-octylamine.
5. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to claim 1, wherein the mass of sodium hypophosphite in step (2) is 1-3 g.
6. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to claim 1, wherein the step (2) is specifically operated as follows: placing sodium hypophosphite in a quartz boat in the central heating zone at the upstream of the two-temperature zone tube furnace, and placing WO3Putting white solid powder of the amine substance hybrid precursor on another quartz boat positioned in a central heating zone at the downstream of the double-temperature zone tubular furnace; introducing argon to remove air, and heating the downstream central heating zone to 3 ℃ at the temperature rise rate of 1-5 ℃/min under atmospheric pressurePreserving heat for 0.5-1.5h at 00-600 ℃, then heating to 650 plus materials at 850 ℃ at the heating rate of 1-10 ℃/min and preserving heat for 1-3h, simultaneously heating the upstream central heating zone to 250 plus materials at 350 ℃ and preserving heat for 1-3 h.
7. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure as claimed in claim 6, wherein argon is introduced to remove air as follows: before the heating process, vacuumizing and ventilating the quartz tube for 2 times under Ar atmosphere to obtain inert atmosphere; and in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 10 s.c.c.m.
8. A carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, characterized by being prepared by the preparation method of any one of claims 1-7.
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