CN115770596A - Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 Preparation method of P mixed material - Google Patents
Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 Preparation method of P mixed material Download PDFInfo
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- CN115770596A CN115770596A CN202211422072.6A CN202211422072A CN115770596A CN 115770596 A CN115770596 A CN 115770596A CN 202211422072 A CN202211422072 A CN 202211422072A CN 115770596 A CN115770596 A CN 115770596A
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- tetrabutyl phosphonium
- phosphonium chloride
- mixed material
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- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 133
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical group [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 13
- 239000002608 ionic liquid Substances 0.000 abstract description 11
- 238000004729 solvothermal method Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 description 41
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical group [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 35
- 238000004140 cleaning Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical group [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 The preparation method of the P mixed material comprises the following steps: step S1: pretreating tetrabutyl phosphonium chloride; step S2: putting a nickel source and a phosphorus source into pretreated tetrabutyl phosphonium chloride, and heating for a certain time at a set temperature in a nitrogen protective atmosphere to obtain Ni 5 P 4 、Ni 2 P is mixed with the material. The invention takes tetrabutyl phosphonium chloride as Ni 5 P 4 、Ni 2 P is used as a solvent of the mixed material, tetrabutyl phosphonium chloride is used as an ionic liquid, and Ni is prepared due to low volatility of the tetrabutyl phosphonium chloride 5 P 4 、Ni 2 Less pressure is formed during the process of P mixing the material,can solve the problem of poor safety caused by high pressure of a closed system due to continuous volatilization of a solvent caused by a solvothermal method so as to safely prepare Ni 5 P 4 、Ni 2 P purpose of the mixed material.
Description
Technical Field
The invention relates to the field of metal materials, in particular to Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 A preparation method of the P mixed material.
Background
The most widely used transition metal phosphide is nickel phosphide. Different phosphorus-nickel ratios have different catalytic activities. The phase state is an important factor affecting the catalytic performance. Therefore, the research on the controllability of the nickel phosphide is particularly important relative to the electrocatalytic performance of the nickel phosphide. Taking the electrolyzed water as an example, the nickel-rich phosphide generally has better hydrogen evolution performance in the electrolyzed water, and the nickel-rich nickel phosphide generally has better oxygen evolution performance in the electrolyzed water. Therefore, the mixture of the nickel-rich phosphide and the nickel-rich nickel phosphide is prepared, and the bifunctional catalyst with good hydrogen evolution and oxygen evolution performances is obtained.
Currently, the most widely used method for preparing nickel phosphide is the solvothermal method. The solvothermal method is developed on the basis of a hydrothermal method, and refers to a synthetic method in which an original mixture is reacted in a closed system such as an autoclave by using an organic or non-aqueous solvent as a solvent at a certain temperature and under the autogenous pressure of the solution. In the process of preparing the nickel phosphide by using the solvothermal method, the pressure of a closed system is higher and higher due to the continuous volatilization of the solvent, so that the closed system can generate huge pressure, and great danger exists in industrial production.
In view of the above, it is necessary to apply Ni in the prior art 5 P 4 、Ni 2 The preparation method of the P-mixed material is improved to solve the above problems.
Disclosure of Invention
The invention aims to disclose Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 Preparation method of P mixed material for solving Ni in prior art 5 P 4 、Ni 2 The preparation method of the P mixed material has high pressure potential safety hazard, so that the development of green and safe Ni is urgently needed 5 P 4 、Ni 2 P mixed material preparation method to achieve safe Ni preparation 5 P 4 、Ni 2 P purpose of the mixed material.
In order to achieve the above object, the present invention provides Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 The preparation method of the P mixed material comprises the following steps:
step S1: pretreating tetrabutyl phosphonium chloride;
step S2: putting a nickel source and a phosphorus source into pretreated tetrabutyl phosphonium chloride, and heating for a certain time at a set temperature in a nitrogen protective atmosphere to obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
As a further improvement of the invention, the nickel source is nickel acetylacetonate, and the phosphorus source is red phosphorus.
As a further improvement of the invention, the mass ratio of the nickel acetylacetonate to the red phosphorus is 100.
As a further improvement of the invention, the mass ratio of the nickel acetylacetonate to the red phosphorus is 100.
As a further improvement of the invention, the nickel source, the phosphorus source and the tetrabutyl phosphonium chloride in the step S2 are placed in a tube furnace to be heated for 1-5 h at the temperature of 300-500 ℃, centrifugation and washing are repeatedly carried out, and drying is carried out to obtain the Ni 5 P 4 、Ni 2 P is mixed with the material.
As a further improvement of the invention, the nickel source, phosphorus source and tetrabutylphosphonium chloride were heated in a tube furnace at 330 ℃ for 2h.
As a further improvement of the present invention, the washing comprises washing 3 to 5 times by using deionized water and absolute ethyl alcohol in this order;
the drying comprises the step of placing the precursor in a vacuum drying oven for continuous drying for 8-24 h.
As a further improvement of the present invention, the pretreatment of the tetrabutyl phosphonium chloride in the step S1 comprises:
the tetrabutyl phosphonium chloride is put into a water bath and heated at 50-100 ℃.
As a further improvement of the invention, the nickel acetylacetonate and the red phosphorus are placed in an excess of tetrabutylphosphonium chloride solvent.
Compared with the prior art, the invention has the beneficial effects that:
by using tetrabutyl phosphonium chloride as a catalyst for preparing Ni 5 P 4 、Ni 2 The solvent of the P mixed material is used, tetrabutyl phosphonium chloride is used as an ionic liquid, and the P mixed material is prepared byIn its low volatility, thereby preparing Ni 5 P 4 、Ni 2 The P mixed material forms smaller pressure in the process, and can solve the problem of poor safety caused by high pressure of a closed system due to continuous volatilization of a solvent in the solvothermal method so as to safely prepare Ni 5 P 4 、Ni 2 P purpose of the hybrid material.
Drawings
FIG. 1 shows Ni based on tetrabutyl phosphonium chloride according to the invention 5 P 4 、Ni 2 A flow chart of a method of preparing the P-mix material;
FIG. 2 shows Ni 5 P 4 、Ni 2 XRD pattern of P-mix material;
FIG. 3 shows Ni 5 P 4 、Ni 2 TEM image of P-hybrid material.
Detailed Description
The present invention is described in detail with reference to the embodiments shown in the drawings, but it should be understood that these embodiments are not intended to limit the present invention, and those skilled in the art should understand that functional, methodological, or structural equivalents or substitutions made by these embodiments are within the scope of the present invention.
Please refer to FIG. 1 and FIG. 3, which disclose a Ni based tetrabutyl phosphonium chloride 5 P 4 、Ni 2 One embodiment of a method for preparing a P hybrid material.
In the examples of the present application, the unit "g" is the unit of weight "g"; the unit "h" is the time unit "hour"; the unit "min" is the time unit "minute"; the unit "KPa" is the pressure unit "kPa"; the unit "DEG C" is the temperature unit "DEG C"; the unit 'nm' is the length unit 'nanometer'; the normal temperature is 25 ℃; the units "g, h" are the rate units "grams per hour".
Referring to FIG. 1, FIG. 1 shows an example of Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 A method for preparing a P-mix material, the method comprising at least steps S1 to S2.
Step S1: pretreating tetrabutyl phosphonium chloride;
step S2: putting a nickel source and a phosphorus source into pretreated tetrabutyl phosphonium chloride, and heating for a certain time at a set temperature in a nitrogen protective atmosphere to obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
Specifically, tetrabutyl phosphonium chloride is first heated in a water bath at 50-100 deg.c to liquefy. Then, taking nickel acetylacetonate, red phosphorus and liquid tetrabutylphosphonium chloride, and uniformly mixing, wherein the mass ratio of the nickel acetylacetonate to the red phosphorus is (100). Then, the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride are heated for 1 to 5 hours in a tube furnace at the temperature of between 300 and 500 ℃, and the centrifugation and the washing are repeatedly carried out, and the drying is carried out to obtain Ni 5 P 4 、Ni 2 P is mixed with the material. A nitrogen atmosphere was formed in a tube furnace during the heating of nickel acetylacetonate, red phosphorus and tetrabutylphosphonium chloride.
Further, in order to remove impurities in the reaction product of nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride, the reaction product was washed 3 to 5 times by using deionized water and absolute ethyl alcohol in sequence. The operation is specifically as follows:
firstly, dispersing a reaction product in deionized water to enable impurities to be dissolved in the deionized water and the reaction product to be immiscible with the deionized water, and placing the reaction product dispersed in the deionized water in a centrifugal machine for centrifugation to enable the reaction product to be precipitated so as to remove the deionized water. Then, the reaction product is dispersed in absolute ethyl alcohol so that impurities in the reaction product are dissolved in the absolute ethyl alcohol and the reaction product is not dissolved in the absolute ethyl alcohol, and the reaction product dispersed in the absolute ethyl alcohol is placed in a centrifugal machine for centrifugation so that the reaction product is precipitated to remove the absolute ethyl alcohol. And then, cleaning the reaction products according to the above operation steps in the order of firstly cleaning with deionized water and then cleaning with absolute ethyl alcohol. In addition, since absolute ethanol is easily volatilized, absolute ethanol is used for washing when the reaction product is washed in the last pass.
Further, the reaction product was placed in a vacuum drying ovenDrying to remove the absolute ethyl alcohol in the reaction product, thereby obtaining Ni 5 P 4 、Ni 2 P is mixed with the material. When the reaction product is dried, the cleaned reverse product is placed in a vacuum drying oven to be dried for 8 to 24 hours under the conditions of normal temperature and relative vacuum degree of 0 to minus 1KPa, so as to remove the ethanol on the surface of the reaction product. Wherein 0KPa represents normal atmospheric pressure.
It should be noted that, before placing nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride in the tube furnace, nitrogen with a purity of 99.99% needs to be introduced into the tube furnace to exhaust air in the tube furnace, so as to avoid oxygen mixing in the reaction process of nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride and prevent the reaction of nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride from being influenced. Introducing nitrogen gas with the purity of 99.99 percent all the time into the tube furnace in which the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride react, and ensuring that the nitrogen gas concentration in the tube furnace is maintained at 99.99 percent all the time. The ultrasonic cleaning type is RQ3200DB, and the ultrasonic frequency is 100KHZ. The model of the tube furnace is OTF-1200X. The model of the vacuum drying oven is DZF-6020. The model of the centrifuge is TGL-16C.
Example 1
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of nickel acetylacetonate and 0.0036g (i.e., 0.0001 mol) of red phosphorus were weighed out and uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride are heated in a tube furnace for 2h at 330 ℃ to form a nitrogen atmosphere in the tube furnace during the heating of the nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried for 12 hours under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so as to remove the absolute ethyl alcohol in the reaction product and obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
Example 2
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of nickel acetylacetonate and 0.0036g (i.e., 0.0001 mol) of red phosphorus were weighed out and uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride are placed in a tube furnace and heated for 1h at the temperature of 300 ℃, and a nitrogen protective atmosphere is formed in the tube furnace during the heating process of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried for 12 hours under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so as to remove the absolute ethyl alcohol in the reaction product and obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
Example 3
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of nickel acetylacetonate and 0.0036g (i.e., 0.0001 mol) of red phosphorus were weighed out and uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride are heated in a tube furnace for 5 hours at 300 ℃, and a nitrogen protective atmosphere is formed in the tube furnace during the heating process of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so that the absolute ethyl alcohol in the reaction product is removed, and Ni is obtained 5 P 4 、Ni 2 P is mixed with the material.
Example 4
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of acetylacetone was weighed outNickel ketone and 0.0036g (i.e., 0.0001 mol) of red phosphorus were uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride are placed in a tube furnace and heated for 2 hours at the temperature of 500 ℃, and a nitrogen protective atmosphere is formed in the tube furnace during the heating process of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried for 12 hours under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so that the absolute ethyl alcohol in the reaction product is removed, and Ni is obtained 5 P 4 、Ni 2 P is mixed with the material.
Example 5
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of nickel acetylacetonate and 0.0072g (i.e., 0.0002 mol) of red phosphorus were weighed out and uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride are heated in a tube furnace for 2h at 330 ℃ to form a nitrogen atmosphere in the tube furnace during the heating of the nickel acetylacetonate, red phosphorus and tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so that the absolute ethyl alcohol in the reaction product is removed, and Ni is obtained 5 P 4 、Ni 2 P is mixed with the material.
Example 6
0.5g (i.e., 0.0017 mol) of tetrabutylphosphonium chloride was weighed into a water bath and heated at 80 ℃ to liquefy the tetrabutylphosphonium chloride. Then, 0.030g (i.e., 0.0001 mol) of nickel acetylacetonate and 0.0018g (i.e., 0.00006 mol) of red phosphorus were weighed out and uniformly dispersed in tetrabutylphosphonium chloride. Secondly, the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride are put into a tube furnace to be heated for 2 hours at 330 ℃ and then added into the acetylacetoneA nitrogen atmosphere is formed in a tube furnace during the heating process of the ketone nickel, the red phosphorus and the tetrabutyl phosphonium chloride. And then, repeatedly performing centrifugation and washing for 3 times according to the step of cleaning the reaction product of the nickel acetylacetonate, the red phosphorus and the tetrabutyl phosphonium chloride to remove impurities in the reaction product. Then, the cleaned reaction product is placed in a vacuum drying oven to be dried under the conditions of normal temperature and relative vacuum degree of-0.85 KPa, so as to remove the absolute ethyl alcohol in the reaction product and obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
In the prior art, a solvothermal method is adopted to prepare nickel phosphide, and in the process of preparing nickel phosphide by using the solvothermal method, the pressure of a closed system is higher and higher due to continuous volatilization of a solvent, so that the closed system can generate huge pressure, and great danger exists in industrial production.
By comparing the standard maps of FIG. 2 and JCPDS cards, the obtained substance is Ni 5 P 4 (JCPDS No. 18-0883) and Ni 2 P (JCPDS No. 03-0953). Ni shown with reference to FIG. 3 5 P 4 、Ni 2 TEM image of P-mixed material revealed that Ni 5 P 4 、Ni 2 The P mixed material is a disc-shaped material with the thickness of about 300 nm. Ni 5 P 4 、Ni 2 The P mixed material belongs to non-noble metal phosphide, and the non-noble metal phosphate has the characteristics of abundant electrochemical active sites, high conductivity, high thermal stability, structural stability and the like, so that the transition metal phosphide is considered as a potential water electrolysis, hydrodesulfurization and deoxidation catalyst. Ni prepared by the method of example 1 to example 6 5 P 4 、Ni 2 The P mixed material has higher electronegativity than the metal atom, so that the electron density of the metal atom can be changed, the electric activity of the metal as an active site is enhanced, and the electrochemical activity of phosphide is enhanced. Ni obtained therefor 5 P 4 、Ni 2 The P mixed material is a potential catalyst for electrolysis of water, hydrodesulfurization and deoxidation.
Ni prepared by the method of example 1 to example 6 5 P 4 、Ni 2 P mixingThe solvent selected by the material is tetrabutyl phosphonium chloride, and the tetrabutyl phosphonium chloride belongs to ionic liquid. Ionic Liquids (ILs) are salt compounds that are liquid at or near room temperature, and are composed of organic cations and inorganic anions with relatively large volume difference, and their high asymmetry makes it difficult for the Ionic Liquids to densely pack or crystallize, so their melting points are low, and they are usually liquid at room temperature. The ionic liquid has the characteristics of nonflammability, low vapor pressure, difficult volatilization, high thermal stability, good conductivity, wide electrochemical potential window, low volatility and the like, and is a recognized green functional medium. For typical ionic liquids, the normal boiling point is related to their saturated vapor pressure at normal atmospheric pressure. Ionic liquids are not volatile at ambient temperatures. When the ionic liquid is continuously heated at 200-300 ℃, a small amount of ionic liquid volatilizes, but the volatilization speed is less than 0.01g and h, and the volatilization speed is very low. Thus, due to its low volatility, ni is being produced 5 P 4 、Ni 2 The P mixed material forms smaller pressure in the process, and can solve the problem of poor safety caused by high pressure of a closed system due to continuous volatilization of a solvent in the process of using a solvothermal method, thereby ensuring that Ni 5 P 4 、Ni 2 Safety in the preparation process of the P mixed material. In addition, the lower vapor pressure also avoids the problem of gas pollution to the environment caused by the volatilization of a large amount of solvent in the prior art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
Claims (9)
1. Ni based on tetrabutyl phosphonium chloride 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized by comprising the following steps:
step S1: pretreating tetrabutyl phosphonium chloride;
step S2: putting a nickel source and a phosphorus source into pretreated tetrabutyl phosphonium chloride, and heating for a certain time at a set temperature in a nitrogen protective atmosphere to obtain Ni 5 P 4 、Ni 2 P is mixed with the material.
2. The tetrabutylphosphonium chloride-based Ni of claim 1 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the nickel source is nickel acetylacetonate, and the phosphorus source is red phosphorus.
3. Tetrabutylphosphonium chloride-based Ni according to claim 2 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the mass ratio of the nickel acetylacetonate to the red phosphorus is (100).
4. Ni based on tetrabutylphosphonium chloride according to claim 3 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the mass of the nickel acetylacetonate and the red phosphorusThe ratio is 100.
5. Ni based on tetrabutylphosphonium chloride according to claim 1 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the nickel source, the phosphorus source and the tetrabutyl phosphonium chloride in the step S2 are placed in a tube furnace to be heated for 1-5 hours at the temperature of 300-500 ℃, centrifugation and washing are repeatedly carried out, and drying is carried out to obtain the Ni 5 P 4 、Ni 2 P is mixed with the material.
6. Ni based on tetrabutylphosphonium chloride according to claim 5 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the nickel source, the phosphorus source and the tetrabutyl phosphonium chloride are placed in a tubular furnace and heated for 2 hours at 330 ℃.
7. The tetrabutylphosphonium chloride-based Ni of claim 5 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the washing comprises washing for 3-5 times by using deionized water and absolute ethyl alcohol in sequence;
the drying comprises the step of placing the precursor in a vacuum drying oven for continuous drying for 8-24 h.
8. Ni based on tetrabutylphosphonium chloride according to claim 1 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the pretreatment of the tetrabutyl phosphonium chloride in the step S1 comprises the following steps:
the tetrabutyl phosphonium chloride is placed in a water bath to be heated at 50-100 ℃.
9. Tetrabutylphosphonium chloride-based Ni according to claim 2 5 P 4 、Ni 2 The preparation method of the P mixed material is characterized in that the nickel acetylacetonate and the red phosphorus are placed in an excessive amount of tetrabutyl phosphonium chloride solvent.
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