CN111514911B - 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 PDF

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CN111514911B
CN111514911B CN202010380130.8A CN202010380130A CN111514911B CN 111514911 B CN111514911 B CN 111514911B CN 202010380130 A CN202010380130 A CN 202010380130A CN 111514911 B CN111514911 B CN 111514911B
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刘勇平
刘威
吕慧丹
耿鹏
庄杨
王子良
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Guilin University of Technology
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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 lamellar WO 3 ·2H 2 O powder: (2) WO 3 Preparation of amine substance hybrid precursor powder: taking WO 3 ·2H 2 Adding the O-block powder and amine substances into a polytetrafluoroethylene reaction kettle, reacting for 24-72h at 100-200 ℃ to obtain white precipitate, centrifugally cleaning with ethanol for several times, and drying to obtain WO 3 White solid powder of amine substance hybrid precursor; (3) preparation of WP @ C: taking sodium hypophosphite as a phosphorus source, and using a double-temperature-control vacuum atmosphere tube furnace to firstly ensure WO 3 Decomposition of amine hybrid precursor into WO x @ C complex, then WO x The @ C complex is phosphorized and reduced to a sheet-like WP @ C electrocatalytic material. The carbon-doped WP nanosheet electrocatalytic material prepared by the method has higher specific surface area and conductivity.

Description

Carbon-doped WP nanosheet electrocatalyst with mesoporous structure and preparation method thereof
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 lamellar WO 3 ·2H 2 O powder: mixing Na 2 WO 4 ·2H 2 Adding 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 WO 3 ·2H 2 O block powder;
(2)WO 3 preparation of amine hybrid precursor powder: get WO 3 ·2H 2 Adding O block powder and amine substance into polytetrafluoroethylene reaction kettle, reacting at 100-200 deg.C for 24-72 hr to obtain white precipitate, centrifuging with ethanol for several times, and drying to obtain WO 3 White 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 WO 3 Decomposition of white solid powder of amine hybrid precursor into WO x @ C complex, then WO x The @ C complex is phosphorized 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: 2-5mol/L.
WO in step (2) 3 ·2H 2 Mass 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 1-3g.
The step (2) is specifically operated as follows: sodium hypophosphite is placed in a quartz boat of a central heating zone at the upstream of a double-temperature-zone tube furnace, and WO is added 3 Putting 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 300-600 ℃ at the temperature rise rate of 1-5 ℃/min under atmospheric pressure, preserving heat for 0.5-1.5h, then heating to 650-850 ℃ at the temperature rise rate of 1-10 ℃/min, preserving heat for 1-3h, simultaneously heating the upstream central heating zone to 250-350 ℃, and preserving heat for 1-3h.
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; the argon flow of the gas path system in the temperature rise process is set to be 100s.c.c.m, and the argon flow is switched to be 10s.c.c.m in the heat preservation stage.
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 -2 The overpotential of time 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 so as to improve the performance, and contributes to promoting the development of the organic-inorganic hybrid catalyst material in the field of electrocatalytic hydrogen evolution.
Drawings
FIG. 1 is an XRD spectrum of the WP @ C nanosheet electrocatalytic hydrogen evolution electrode material obtained in example 1 of the invention.
FIG. 2 is an SEM image of the electro-catalytic hydrogen evolution electrode material of WP @ C nanosheets obtained in example 1 of the present invention.
FIGS. 3 and 4 are BET diagrams of the electro-catalytic hydrogen evolution electrode material of WP @ C nanosheet obtained in example 1 of the present invention.
FIG. 5 is a LSV curve diagram of the electro-catalytic hydrogen evolution electrode material of WP @ C nanosheet 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 so that those skilled in the art can better understand and implement the technical solutions of the present invention.
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 WO 3 ·2H 2 O powder: 10mL of sodium tungstate Na 2 WO 4 ·2H 2 Solution 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 WO 3 ·2H 2 O block powder.
(2)WO 3 Preparation of n-propylamine hybrid precursor powder: 0.4g of WO lumps are weighed out 3 ·2H 2 Adding 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. 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 precipitate 3 N-propylamine hybrid precursor.
(3) Preparation of WP @ C: the samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. Drying the obtained WO 3 The white solid powder of the n-propylamine precursor is placed 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 WO x a/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 NaH 2 PO 2 Heating to 300 ℃ at the upstream of the tube furnace at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling after the reaction is completed. Gas at temperature rising stageThe channel system was ventilated with an argon flow of 100s.c.c.m, and the flow rate was 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 WO 3 ·2H 2 O powder: 10mL of Na tungstate 2 WO 4 ·2H 2 Solution 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 WO 3 ·2H 2 O block powder.
(2)WO 3 Preparation of n-butylamine hybrid precursor powder: 0.8g of block WO is weighed 3 ·2H 2 Adding O into a 50mL polytetrafluoroethylene reaction kettle liner, weighing 32mL n-butylamine by using a dried measuring cylinder, pouring the n-butylamine into the reaction kettle, putting the reaction kettle into an oven at 180 ℃ for reaction for 48 hours, taking out the reaction kettle, and naturally cooling the reaction kettle 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 precipitate 3 N-butylamine hybrid precursor.
(3) Preparation of WP @ C: the samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. Drying the obtained WO 3 Putting 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 WO x a/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 NaH 2 PO 2 At the upstream of the tube furnace, the temperature is raised to 300 ℃ at a rate of 5 ℃/minKeeping the temperature at the temperature for 2 hours, and naturally cooling after the reaction is completed. The gas circuit system in the temperature rise stage is aerated with argon flow of 100s.c.c.m, and the flow in the reaction stage is switched to 10s.c.c.m. And taking out the sintered WP @ C sample after the tube furnace is cooled to 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 WO 3 ·2H 2 O powder: 10mL of Na tungstate 2 WO 4 ·2H 2 Solution O (1.0M) was added to 90mL of HCl solution (3.0M) and magnetically stirred in an ice-water bath for 30min, whereupon an immediate white precipitate was observed, which gradually turned yellow as the reaction proceeded. Centrifuging the obtained yellowish suspension, washing with deionized water for several times until the pH is about 7, and drying the yellowish suspension with a freeze dryer to obtain a layered solid, namely, lamellar WO 3 ·2H 2 O block powder.
(2)WO 3 Preparation of n-octylamine hybrid precursor powder: 0.4g of WO lumps are weighed out 3 ·2H 2 Adding O into a 50mL polytetrafluoroethylene reaction kettle liner, weighing 16mL of n-octylamine by using a dried measuring cylinder, pouring into the reaction kettle, putting the reaction kettle into a 160 ℃ oven for reaction for 72 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 precipitate 3 A 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 WO 3 And/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 WO x a/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 NaH 2 PO 2 Heating to 300 ℃ at the upstream of the tube furnace at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling after the reaction is completed. The gas circuit system in the temperature rise stage is aerated with argon flow of 100s.c.c.m, and the flow in the reaction stage is switched to 10s.c.c.m. 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 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 temperature 2 SO 4 And 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 for WP @ c occur at 2 θ =21.1 °,28.7 °,31.1 °,42.9 °,44.6 ° and 46.5 °, perfectly matching the orthorhombic phase WP standard card (JCPDS No. 29-1364), indicating that the samples prepared are 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 5.59m 2 ·g -1 Is 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 electrocatalytic hydrogen evolution performance in acidity, and the current density is 10 mA-cm -2 The overpotential is 190mV, and the corresponding Tafel slope is 108mV dec -1 。
The above embodiments are described in detail for different implementations of the present invention, but the implementation manner of the present invention is not limited thereto, and those skilled in the art can achieve the object 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 protection scope of the present invention, and the specific protection scope is subject to the claims.

Claims (6)

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 WO 3 ·2H 2 O powder: mixing Na 2 WO 4 ·2H 2 Adding 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 WO 3 ·2H 2 O block powder; wherein, the concentration of sodium tungstate solution is: 1-3mol/L, hydrochloric acid solution concentration: 2-5mol/L;
(2)WO 3 preparation of amine substance hybrid precursor powder: taking WO 3 ·2H 2 Adding the O-block powder and amine substances into a polytetrafluoroethylene reaction kettle, reacting for 24-72h at 100-200 ℃ to obtain white precipitate, centrifugally cleaning with ethanol for several times, and drying to obtain WO 3 White solid powder of amine hybrid precursor; among them, WO 3 ·2H 2 Mass of O powder: 0.1-2g, volume of amine substance: 4-80mL;
(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 WO 3 Decomposition of white solid powder of amine substance hybrid precursor into WO x @ C complex, then WO x The @ C complex is phosphorized 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 amine substance in step (2) is one of n-propylamine, n-butylamine, and n-octylamine.
3. 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 (3) is 1-3g.
4. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to claim 1, characterized in that step (3) is specifically operated as follows: sodium hypophosphite is placed in a quartz boat of a central heating zone at the upstream of a double-temperature-zone tube furnace, and WO is added 3 Putting 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 300-600 ℃ at the temperature rise rate of 1-5 ℃/min under atmospheric pressure, preserving heat for 0.5-1.5h, then heating to 650-850 ℃ at the temperature rise rate of 1-10 ℃/min, preserving heat for 1-3h, simultaneously heating the upstream central heating zone to 250-350 ℃, and preserving heat for 1-3h.
5. The preparation method of the carbon-doped WP nanosheet electrocatalyst with the mesoporous structure according to claim 4, 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; the argon flow of the gas path system in the temperature rise process is set to be 100s.c.c.m, and the argon flow is switched to be 10s.c.c.m in the heat preservation stage.
6. A carbon-doped WP nanosheet electrocatalyst with a mesoporous structure, characterized by being prepared by the preparation method of any one of claims 1-5.
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