CN113652698B - Tungsten-doped nickel phosphide dual-functional catalytic material with crossed nano-sheet structure - Google Patents
Tungsten-doped nickel phosphide dual-functional catalytic material with crossed nano-sheet structure Download PDFInfo
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Abstract
The invention discloses a tungsten-doped nickel phosphide dual-functional catalytic material with a cross nano-sheet structure, which is prepared by adopting a hydrothermal phosphorization method, and is modified by adopting a heteroatom doping strategy, and finally the obtained tungsten-doped nickel phosphide dual-functional catalytic material has excellent performances in HER, OER and full hydrolysis.
Description
Technical Field
The invention relates to the technical field of catalytic material production, in particular to a tungsten doped nickel phosphide dual-functional catalytic material with a cross nano-sheet structure.
Background
At present, due to the growing prominence of shortage of non-renewable energy sources and environmental pollution problems, the search and development of new energy sources that are environmentally friendly has become a hot spot of interest to researchers. In recent years, the development and utilization of hydrogen energy have attracted considerable attention from researchers because of its excellent characteristics of no pollution, high heat value, and the like. Thus, various hydrogen production technologies have been developed. Among the numerous hydrogen production processes, electrolytic water hydrogen production is a clean and efficient method of producing hydrogen, the reaction process of which includes Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER).
The traditional catalysts for hydrogen evolution reaction and oxygen evolution reaction are Pt-based and Ir/Ru catalysts respectively, and the catalysts are noble metal catalysts and have the defects of scarcity and high price, so that the wide application of the catalysts in the actual water electrolysis process is limited to a great extent. It is seen that research and development of a non-noble metal catalytic material (such as nickel-based) which has high storage capacity, low price, excellent performance and wide application in industrial production is important for the water electrolysis process.
The transition metal element has the advantages of high storage amount and low price, so the transition metal element can be used as an effective substitute of a noble metal catalyst. However, the performance of the transition metal-based catalyst is far less than that of the traditional noble metal catalyst, and the transition metal-based catalyst needs to be modified to improve the performance and the stability of the transition metal-based catalyst. Generally, doping of heteroatoms is a better method of modifying transition metal-based catalysts. In addition, transition metal based catalysts are difficult to co-act in the same medium due to the incompatibility of HER and OER activity and stability. Therefore, developing a bifunctional catalytic material for HER and OER has good application prospect.
Disclosure of Invention
The invention aims to provide a tungsten doped nickel phosphide dual-functional catalytic material with a cross nano-sheet structure, which can be used for replacing a traditional noble metal catalyst, and has excellent hydrogen evolution catalytic activity and oxygen evolution catalytic activity and stronger catalytic stability in alkaline electrolyte.
The technical scheme adopted for solving the technical problems is as follows:
the tungsten doped nickel phosphide dual-functional catalytic material with the crossed nano sheet structure is prepared by the following steps:
step one, hydrothermally synthesizing a tungsten nickel hydroxide precursor growing on carbon cloth:
adding urea, ammonium fluoride, nickel nitrate and ammonium metatungstate into deionized water, and fully stirring to obtain a uniformly mixed precursor solution; transferring the precursor solution and the pretreated carbon cloth to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and obtaining a tungsten nickel hydroxide precursor growing on the carbon cloth through hydrothermal reaction;
step two, phosphating:
and respectively placing sodium hypophosphite and tungsten nickel hydroxide precursors growing on the carbon cloth at the upstream and downstream of the porcelain boat, then placing the porcelain boat into a tubular furnace for calcination, and introducing argon as a protective gas in the heating process to finally obtain the tungsten doped nickel phosphide dual-functional catalytic material with the cross nano-sheet structure.
The invention adopts carbon cloth as a conductive substrate and a growth substrate of the nano-sheet catalytic material, and the prepared tungsten-doped nickel phosphide dual-functional catalytic material has a crossed and compact nano-sheet structure on carbon cloth fibers.
The nano-sheet is obtained by in-situ growth on carbon cloth through hydrothermal reaction. The conventional nickel-based catalyst has poor catalytic performance, and the catalytic performance of the invention is greatly improved; the catalytic performance is improved because compared with an undoped nickel phosphide catalyst, the nano-sheet of the tungsten-doped nickel phosphide bifunctional catalytic material is smaller in size and denser, and the compact nano-sheet has larger specific surface area, so that more active sites are exposed, and the catalytic performance is improved.
Because a plurality of transition metal catalysts can not realize HER and OER catalytic reactions simultaneously in the same medium at present, the full water decomposition test of the catalytic material obtained by the invention proves that the catalytic material can realize HER and OER catalytic reactions simultaneously in the same medium, and has better activity and stability.
The preparation method provided by the invention has the advantages of simplicity, easiness and easiness in implementation, and modification is performed by adopting a heteroatom doping strategy, so that the finally obtained tungsten-doped nickel phosphide dual-functional catalytic material has excellent performances in terms of HER, OER and full hydrolysis.
The pretreatment method of the carbon cloth comprises the following steps: transferring the sheared carbon cloth and concentrated nitric acid into a stainless steel autoclave with polytetrafluoroethylene, preserving heat for 2-3h at 90+/-5 ℃, and respectively carrying out ultrasonic cleaning by using ethanol and deionized water after finishing. The mass concentration of the concentrated nitric acid is 65-70%.
The precursor solution comprises the following raw materials in proportion: 10-20mM urea, 5-10 mM ammonium fluoride, 1.5-2.5 mM nickel nitrate, 0.005-0.025 mM ammonium metatungstate, 30-40 mL deionized water.
Preferably, ammonium metatungstate: nickel nitrate: ammonium fluoride: the molar ratio of urea is 0.1:1:3:5.
the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 110+/-10 ℃ and the hydrothermal time is 5-8 h.
The flow rate of argon is controlled between 140 and 160sccm.
Sodium hypophosphite: the molar ratio of the nickel nitrate is 1.7-3:1.
The phosphating process is divided into three stages: the first stage: heating from room temperature to 350+ -50deg.C at a heating rate of 4-6deg.C/min; and a second stage: the heat preservation stage, wherein the temperature is kept constant at 350+/-50 ℃ for 2-3h, and the third stage: naturally cooling to room temperature.
The beneficial effects of the invention are as follows:
1. the tungsten-doped nickel phosphide difunctional catalytic material can reach 10 mA/cm in 1M KOH alkaline medium only by 71 mV overpotential in the Hydrogen Evolution Reaction (HER) process 2 Is driven by a voltage of only 308 mV during Oxygen Evolution (OER) of 20 mA/cm 2 Is used for the current density of the battery. In addition, 20 mA/cm was reached during the complete water dissolution in alkaline medium 2 The voltage required for the current density of (a) is only 1.55. 1.55V. Meanwhile, the catalyst has extremely strong stability, and can ensure that the stability is not reduced in at least 40 h.
2. The raw materials of the invention adopt non-noble metal elements with abundant storage capacity and low price, in addition, the preparation method combines two simple reaction processes of hydrothermal and phosphating, the repeatability is high, and the performance of the finally obtained bifunctional catalyst is superior to that of the nickel phosphide catalyst prepared under the same condition. It can be seen that this is a very efficient and stable hydrogen evolution catalytic material, and has great potential for industrial application and commercial value.
Drawings
FIG. 1 is an X-ray diffraction (XRD) test spectrum of a tungsten-doped nickel phosphide bifunctional catalytic material having a cross-nanosheet structure prepared in accordance with the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of a tungsten doped nickel phosphide bifunctional catalytic material with a cross-nanosheet structure prepared in accordance with the present invention.
FIG. 3 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of a tungsten doped nickel phosphide dual-function catalytic material with a cross-nano-sheet structure prepared in accordance with the present invention.
Fig. 4 is an LSV contrast curve and a stability test curve corresponding to HER in a 1M KOH alkaline environment for a tungsten doped nickel phosphide bifunctional catalytic material having a cross-nanosheet structure prepared in accordance with the present invention.
FIG. 5 is a comparison curve and stability test curve of LSV corresponding to OER in 1M KOH alkaline environment of a tungsten-doped nickel phosphide bifunctional catalytic material with a cross-nano-sheet structure prepared by the invention.
FIG. 6 is a comparison curve and stability test curve of LSV corresponding to full hydrolysis in 1M KOH alkaline environment of a tungsten-doped nickel phosphide bifunctional catalytic material with a cross-nanosheet structure prepared by the present invention.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples.
In the present invention, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Ammonium metatungstate hydrate, ammonium fluoride, urea and sodium hypophosphite were purchased from Shanghai Ala Biochemical technologies Co., ltd; nickel acid hexahydrate was purchased from Shanghai Melin Biotechnology Co., ltd; carbon cloth was purchased from taiwan carbon technologies inc.
Pretreatment of carbon cloth: transferring the sheared carbon cloth and concentrated nitric acid (65% -70%) into a stainless steel autoclave with polytetrafluoroethylene, preserving heat for 2-3h at 90+/-5 ℃, and respectively carrying out ultrasonic cleaning by using ethanol and deionized water after finishing.
Example 1:
in the first step, a hydrothermal reaction is carried out, and 10 mM CH is weighed 4 N 2 O (Urea), 6 mM NH 4 F (ammonium fluoride), 2 mM Ni (NO) 3 ) 2 (Nickel nitrate hexahydrate), 0.013 mM (NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 O (ammonium meta-tungstate hydrate) is dissolved in 30 mL deionized water, uniform precursor solution is obtained after stirring for 30 min, the precursor solution is transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining, pretreated carbon cloth (1 cm multiplied by 4 cm) is added, and the reaction kettle is put into a blast drying box for hydrothermal reaction at 120 ℃ for 6 h. After the hydrothermal process was completed, the mixture was rinsed with deionized water and dried at 60℃for 6 h.
The second step is a phosphating reaction, 0.5g NaH is added 2 PO 2 (sodium hypophosphite) and carbon cloth with precursors are placed upstream and downstream of the porcelain boat respectively, and then the porcelain boat is placed into a tube furnace for calcination. And (3) setting a phosphating program: the first stage: the temperature rising rate is 5 ℃/min from room temperature to 350 ℃, and the second stage is as follows: at 350 ℃,2 h is kept warm, and the third stage: naturally cooling to room temperature. Argon is required to be introduced as a protective gas in the whole process of the phosphating reaction.
Example 2:
in the first step, a hydrothermal reaction is carried out, and 15 mM CH is weighed 4 N 2 O (Urea), 8 mM NH 4 F (ammonium fluoride), 2 mM Ni (NO) 3 ) 2 (Nickel nitrate hexahydrate), 0.01 mM (NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 O (ammonium meta-tungstate hydrate) is dissolved in 30 mL deionized water, uniform precursor solution is obtained after stirring for 30 min, the precursor solution is transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining, pretreated carbon cloth (1 cm multiplied by 4 cm) is added, and the reaction kettle is put into a blast drying box for hydrothermal reaction at 120 ℃ for 6 h. After the hydrothermal process was completed, the mixture was rinsed with deionized water and dried at 60℃for 6 h.
The second step is a phosphating reaction, 0.4g NaH is added 2 PO 2 (sodium hypophosphite) and carbon cloth with precursors are placed upstream and downstream of the porcelain boat respectively, and then the porcelain boat is placed into a tube furnace for calcination. And (3) setting a phosphating program: the first stage: the temperature rising rate is 5 ℃/min from room temperature to 350 ℃, and the second stage is as follows: at 350 ℃,2 h is kept warm, and the third stage: naturally cooling to room temperature. Argon is required to be introduced as a protective gas in the whole process of the phosphating reaction.
Example 3:
in the first step, a hydrothermal reaction is carried out, and 20mM CH is weighed 4 N 2 O (Urea), 10 mM NH 4 F (ammonium fluoride), 2 mM Ni (NO) 3 ) 2 (Nickel nitrate hexahydrate), 0.017. 0.017 mM (NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 O (ammonium meta-tungstate hydrate) dissolved in 30 mL to removeAnd (3) adding ionized water, stirring for 30 min to obtain a uniform precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding pretreated carbon cloth (1 cm multiplied by 4 cm), and placing the reaction kettle into a blast drying box for hydrothermal reaction at 120 ℃ for 6 h. After the hydrothermal process was completed, the mixture was rinsed with deionized water and dried at 60℃for 6 h.
The second step is a phosphating reaction, 0.5g NaH is added 2 PO 2 (sodium hypophosphite) and carbon cloth with precursors are placed upstream and downstream of the porcelain boat respectively, and then the porcelain boat is placed into a tube furnace for calcination. And (3) setting a phosphating program: the first stage: the temperature rising rate is 5 ℃/min from room temperature to 400 ℃, and the second stage is as follows: at 400 ℃,2 h is kept warm, and the third stage: naturally cooling to room temperature. Argon is required to be introduced as a protective gas in the whole process of the phosphating reaction.
FIG. 1 is an X-ray diffraction (XRD) test pattern of the catalytic material prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) characterization image of the catalytic material prepared in example 1 of the present invention, from which it can be seen that the catalytic material exhibits cross-nanoplatelets on a carbon cloth.
FIG. 3 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) characterization image of the catalytic material prepared in example 1 of the present invention, in which the catalytic material is seen as lattice fringes and defects.
Fig. 4 is a LSV graph of Hydrogen Evolution Reaction (HER) in alkaline electrolyte (1M KOH) and a stability test curve of the catalytic material prepared in example 1 of the present invention, which can be obtained to have excellent catalytic activity and stability in alkaline environment.
Fig. 5 is a LSV graph of Oxygen Evolution Reaction (OER) in alkaline electrolyte (1M KOH) and a stability test curve of the catalytic material prepared in example 1 according to the present invention, which can be obtained to have excellent catalytic performance in OER.
Fig. 6 is an LSV graph and a stability test curve of the catalytic material with a nano-sheet structure prepared in example 1 of the present invention for full water dissolution in alkaline electrolyte (1M KOH), and compared with a nickel phosphide catalytic material, the tungsten doped nickel phosphide dual-functional catalytic material has better full water dissolution activity.
The above examples are preferred methods of implementation obtained through long-term experiments, and the raw material proportion and the phosphating process can be changed according to actual requirements, so that the method can be implemented within the scope of the embodiments described in the claims.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (3)
1. The tungsten-doped nickel phosphide full-hydrolysis catalytic material with the cross nano-sheet structure is characterized by being prepared by the following steps:
step one, hydrothermally synthesizing a tungsten nickel hydroxide precursor growing on carbon cloth:
adding urea, ammonium fluoride, nickel nitrate and ammonium metatungstate into deionized water, and fully stirring to obtain a uniformly mixed precursor solution; transferring the precursor solution and the pretreated carbon cloth to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and obtaining a tungsten nickel hydroxide precursor growing on the carbon cloth through hydrothermal reaction;
step two, phosphating:
respectively placing sodium hypophosphite and tungsten nickel hydroxide precursors growing on carbon cloth at the upstream and downstream of a porcelain boat, then placing the porcelain boat into a tubular furnace for calcination, and introducing argon as a protective gas in the heating process to finally obtain the tungsten doped nickel phosphide full-water-splitting catalytic material with a cross nano-sheet structure;
the precursor solution comprises the following raw materials in proportion: 10-20mM of urea, 5-10 mM of ammonium fluoride, 1.5-2.5 mM of nickel nitrate, 0.005-0.025 mM of ammonium metatungstate and 30-40 mL of deionized water;
sodium hypophosphite: the molar ratio of the nickel nitrate is 1.7-3:1;
the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 110+/-10 ℃ and the hydrothermal time is 5-8 h;
the phosphating process is divided into three stages: the first stage: heating from room temperature to 350+ -50deg.C at a heating rate of 4-6deg.C/min; and a second stage: the heat preservation stage, wherein the temperature is kept constant at 350+/-50 ℃ for 2-3h, and the third stage: naturally cooling to room temperature.
2. The tungsten-doped nickel phosphide full-hydrolysis catalytic material with a cross-nano sheet structure as set forth in claim 1, wherein the pretreatment method of the carbon cloth is as follows: transferring the sheared carbon cloth and concentrated nitric acid into a stainless steel autoclave with polytetrafluoroethylene, preserving heat for 2-3h at 90+/-5 ℃, and respectively carrying out ultrasonic cleaning by using ethanol and deionized water after finishing.
3. The tungsten-doped nickel phosphide full water-splitting catalytic material with cross-nano sheet structure according to claim 1, wherein the flow rate of argon is controlled to 140-160sccm.
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