CN106179434A - A kind of porous Ni P based compound and preparation method thereof - Google Patents
A kind of porous Ni P based compound and preparation method thereof Download PDFInfo
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- CN106179434A CN106179434A CN201610518947.0A CN201610518947A CN106179434A CN 106179434 A CN106179434 A CN 106179434A CN 201610518947 A CN201610518947 A CN 201610518947A CN 106179434 A CN106179434 A CN 106179434A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 19
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 8
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- -1 nickel phosphorus compound Chemical class 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910001096 P alloy Inorganic materials 0.000 description 12
- JUWOETZNAMLKMG-UHFFFAOYSA-N [P].[Ni].[Cu] Chemical compound [P].[Ni].[Cu] JUWOETZNAMLKMG-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 9
- 229910018104 Ni-P Inorganic materials 0.000 description 8
- 229910018536 Ni—P Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 241000258149 Hemicentrotus Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000258125 Strongylocentrotus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/653—
-
- B01J35/657—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of porous Ni P based compound and preparation method thereof, belong to the synthesis technical field of nickel phosphorus compound.The porous Ni P based compound of the present invention, the mol ratio of Ni Yu P is 2 2.7:1；Being a kind of spongy particles, particle diameter is 10 50 μm, and aperture is 0.6 3.5 μm.Possessing " spongy " pattern of uniqueness, hole therein is not through hole, and its specific surface area significantly improves.The preparation method of the present invention uses metal bath as reaction environment, the apparatus for melting metal using routine realizes the controlled preparation to metal phosphide, and by nickel phosphorous atomic ratio in adjustment alloy system, the design to nickel phosphorus series compound product can be realized, reduce production cost, enormously simplify generation process, shorten the production time, improve productivity.It also avoid the reaction condition that poisonous phosphorus source, high pressure etc. are harsh simultaneously.
Description
Technical field
The present invention relates to a kind of porous Ni P based compound and preparation method thereof, belong to the synthetic technology neck of nickel phosphorus compound
Territory.
Background technology
Binary that metal phosphide is metal to be formed with phosphorus and the general name of multi-element compounds.P elements can with in periodic chart
Most metals forms multiple phosphide, and its chemical bond formed is the most different.Simultaneously as the radius of phosphorus atoms is relatively
Greatly, in the way of filling, occupy the intracell of metallic atom, thus make it have the semiconductive of uniqueness, magnetic, catalytic
With electric property etc..Meanwhile, it is widely used in hydrodesulfurization, denitrogenation aspect, at stone as a kind of good catalyst
The oil chemical field such as processing is succeeded application.Unifining process is commonly used Ni2The transition metal phosphatization of P, CoP, MoP etc.
Thing.They in HDN and HDS reacts activeness order as described in below: CoP < MoP < Ni2P.Single with regard to its catalytic performance
Speech, transition metal phosphide can be crossed the hydrogenation reaction to alkynes, alkene etc. and play catalytic action.Ni-P alloy as catalyst instead
During Ying Zhongqi catalytic action, higher than switching rate during pure metal Ni effect.
Ni-P compound is the one in transition metal phosphide, can form the chemical combination of multiple atom ratio between two kinds of elements
Thing, such as Ni12P5、Ni2P、Ni5P2Etc..Owing to it has superior performance, it is referred to as the focus of research in recent years.For phosphide
For, the incorporation of phosphorus atoms makes the d band of W metal atom shrink, and causes the density of fermi level to increase, and then promotes it relatively
Other catalyst (such as nitride, sulfide, carbide etc.) shows higher chemical stability, catalysis activity, anti-carbon
Poisoning performance anti-with resistant to sulfur, it also shows the performance of brilliance at aspects such as electricity, magnetics, optics.Such as, Ni12P5、Ni2P
There is good photocatalytic activity, can photocatalytically degradating organic dye；Compared with traditional electrode material, phosphide also has greatly
The advantages such as capacitance, discharge cycle length and good cycle, are the negative materials of preferable lithium ion battery.
During Ni-P compound uses as catalyst, its catalytic performance is closely related with its pattern, different-shape
The catalytic performance of Ni-P compound difference, even notable difference.The pattern of presently disclosed Ni-P compound includes close
Pile up nanosphere (Yan Jingsen, Hubei Province Yongsheng, Tian Yasai, Zhang Chuan, Zhang Heng, the controllable synthesis method of a kind of nickel phosphide nano material,
Application number: 201510308950.5), Hemicentrotus seu Strongylocentrotus shape hollow-core construction (Ni Yonghong, Wei Jieding, a kind of micron order nickel phosphide material and
Preparation method and use, 201310594337.5), hollow core shell structure (Liu Shuling, Lin Yang, Tong Jianbo, Cheng Fangling, Yi Zhongzhong
The preparation method of empty nucleocapsid structure nickel phosphide, 201410384664.9), particle diameter is about the microspheroidal (Ni of 2-5 μm12P5Microsphere
Solvent-thermal process and sign, Liu Shuling, Li Shu, Shi Qiangqiang, Li Miaomiao, functional material, 2012,43(14): 1885-1893).
Summary of the invention
It is an object of the invention to provide a kind of Ni-P compound possessing new pattern and preparation method thereof, to improve
The catalytic performance of Ni-P compound.
A kind of porous Ni P based compound, the mol ratio of Ni Yu P is 2-2.7:1；Being a kind of spongy particles, particle diameter is
10-50 μm, aperture is 0.6-3.5 μm.
The porous Ni P based compound of the present invention possesses " spongy " pattern of uniqueness, and hole therein is not through hole, its ratio
Surface area significantly improves.
The preparation method of above-mentioned porous Ni P based compound, comprises the following steps:
(1) using copper phosphorus intermediate alloy as phosphorus source, copper-nickel intermediate alloy or industrial pure ni as nickel source, vacuum arc is used to melt
Furnace carries out melting, forms metal mother's ingot；Copper, the mol ratio of nickel are 2.18-5.90:1；
(2) utilize high vacuum single roller to revolve system of quenching and strip is quenched in the rotation of metal mother's ingot；
(3) being placed in ferric chloride solution by strip and carry out corrosion treatmentCorrosion Science, gained powder is Ni P based compound；Ferric chloride solution
Concentration be 1.5 4.5mol/L, etching time is 1 10 hours, and corrosion temperature scope is 25 DEG C 95 DEG C.
Above-mentioned preparation method, copper phosphorus intermediate alloy used, the mass percent of its component is: phosphorus 6.0 15.0%, surplus
For copper；Copper nickel intermediate alloy used, the mass percent of its component is: nickel 30.0 50.0%, and surplus is copper.
Above-mentioned preparation method, alloy mother's ingot uses vacuum arc melting furnace melt back 25 times, it is ensured that nickel and phosphorus in female ingot
Reaction is completely, uniformly.
Above-mentioned preparation method, in step 2, to get rid of the rotating speed of band machine rotating speed the fastest for melt spinning method, and melt spinning method makes its cooling speed
Spending the fastest, in the strip formed, structure is the most tiny, and after corrosion treatmentCorrosion Science, relative aperture will be the least；It is preferred, therefore, that, set single
The roller range of speeds is 1,000 2500 revs/min.
Above-mentioned preparation method, the particle diameter of porous Ni-P based compound is affected by degree of cleaning, it is preferred that use distillation
Water, dehydrated alcohol carry out ultrasonic waves for cleaning to step 3 gained powder 37 times, centrifugal 35 times, dried 13 hours；Centrifugal
Rotating speed is 6,000 15000 revs/min；Baking temperature is 25 DEG C 90 DEG C.
The preparation method of the porous Ni P based compound of the present invention:
Firstly, it is necessary to strictly control nickel, copper mass ratio in raw material, otherwise, it is impossible to obtain the product of the present invention.Secondly, can obtain
Under conditions of obtaining the product of the present invention, nickel, phosphorus mass ratio will not produce impact to " spongy pattern ".Again, strict control is needed
Etching time processed, etching time is long, then cannot obtain the product of the present invention.The preparation of the porous Ni P based compound of the present invention
Method, required etching time is shorter.
Beneficial effect
Porous Ni its novel in shape of P based compound of the present invention, its hole is not through hole, and possesses its specific surface area and significantly improve
Advantage；Thus promote its hydrodesulfurization (HDS), hydrodenitrogeneration (HDN), hydrogenation deoxidation (HDO) activity, photocatalysis performance
Promote.
The preparation method of the present invention uses metal bath as reaction environment, uses the apparatus for melting metal of routine to realize right
The controlled preparation of metal phosphide, and by nickel phosphorous atomic ratio in adjustment alloy system, can realize nickel phosphorus series compound
The design of product, reduces production cost, enormously simplify generation process, shortens the production time, improves productivity.The most also
Avoid the reaction condition that poisonous phosphorus source, high pressure etc. are harsh.The method simple process is easily-controllable, need not the instruments such as autoclave
And dried under vacuum or protective atmosphere, and react that required time is short, phosphide output capacity high, no coupling product pollutes.
The preparation method of the present invention, possesses etching time short, to nickel and the less demanding advantage of phosphorus ratio.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the Cu 17.1Ni 4.5P strip of embodiment 1 preparation；
Fig. 2 is the scanning electron microscopic picture of the Ni P powder body of embodiment 1 preparation；
Fig. 3 is the scanning electron microscopic picture of the Ni P powder body of embodiment 2 preparation；
Fig. 4 is the scanning electron microscopic picture of the Ni P powder body of embodiment 3 preparation.
Detailed description of the invention
Embodiment 1
(1) industrial pure copper 33.6%, copper nickel intermediate alloy 34.26%, the mass percent of copper phosphorus intermediate alloy 32.14% are pressed
Weigh raw material.Wherein in copper nickel intermediate alloy, the mass percent of copper is 50.0%, and the mass percent of nickel is 50.0%；Copper phosphorus
In intermediate alloy, the mass percent of copper is 86.0%, and the mass percent of phosphorus is 14.0%.
(2) in vacuum arc melting furnace, copper nickel-phosphorus alloy ingot is founded.Specifically comprise the following steps that and the raw material prepared is put
In the copper crucible of electric arc furnace, utilize the high-temperature electric arc heating melt raw material that tungsten electrode head and the electric discharge of alloy mother's ingot are formed, repeatedly melt
Refining obtains female ingot.Here, melt back 3 times is uniform to ensure melting.Every time before melting, striking, will be by copper nickel-phosphorus alloy
The oxide skin of female ingot surface polishes off, and has ensured that striking is abundant, melting is uniform.
(3) gained copper nickel-phosphorus alloy mother's ingot carry out fine vacuum melt spinning method process make strip.Melting is closed uniformly
The female ingot of gold is put in the foraminate quartz test tube of bottom belt after cutting into alloy block, treats that stove internal gas pressure reduces to 10-3 Below Pa, fills
Enter a certain amount of argon, by copper induction coil the alloy block in quartz test tube quickly heated and be allowed to melt, after alloy melting
Heating 1 minute, pressing spray to cast valve under the air pressure of 0.06 ~ 0.08 MPa by alloy melt spray to cast to rotating speed is 1200 revs/min
Copper roller on, strip can be formed.
(4) gained copper nickel-phosphorus alloy strip is placed in 25 DEG C, in the ferric chloride solution of 1.5mol/L, freely corrodes 10 little
Time.Utilize dehydrated alcohol, deionized water to carry out ultrasonic waves for cleaning in gained powder subsequently, utilize high speed centrifuge to carry out thing and divide mutually
From, centrifuge speed is set as 6000 revs/min, is placed in by gained powder in the drying baker of 50 DEG C 3 hours, obtains Ni12P5Powder
End.This Ni12P5Product presents porous spongy structure；Relative to the particle of equal particle diameter, its specific surface area can improve 47.8%.
Ni12P5Having photocatalytic degradation effect to Congo red, be added into Congo red organic dye solution, solution concentration is chosen to be
1×10-5Mol/L, is placed in camera bellows after ultrasonic 30min, reaches adsorption-desorption balance, uses uviol lamp to drop as light source
Solve test.It is found by experiment that, the Ni after 90min, prepared by the present embodiment12P5The degradation rate of Congo red be can reach 94.5%
Above；Under same light catalytic condition, improve 4.61-7.39% than the degradation rate of the nickel phosphide of other patterns.
Embodiment 2
(1) industrial pure copper 5.39%, copper nickel intermediate alloy 57.11%, the mass percent of copper phosphorus intermediate alloy 37.5% are pressed
Weigh raw material.Wherein in copper nickel intermediate alloy, the mass percent of copper is 55.0%, and the mass percent of nickel is 45.0%；Copper phosphorus
In intermediate alloy, the mass percent of copper is 88.0%, and the mass percent of phosphorus is 12.0%.
(2) in vacuum arc melting furnace, copper nickel-phosphorus alloy ingot is founded.Specifically comprise the following steps that and the raw material prepared is put
In the copper crucible of electric arc furnace, utilize the high-temperature electric arc heating melt raw material that tungsten electrode head and the electric discharge of alloy mother's ingot are formed, repeatedly melt
Refining obtains female ingot.Here, melt back 4 times is uniform to ensure melting.Every time before melting, striking, will be by copper nickel-phosphorus alloy
The oxide skin of female ingot surface polishes off, and has ensured that striking is abundant, melting is uniform.
(3) gained copper nickel-phosphorus alloy mother's ingot carry out fine vacuum melt spinning method process make strip.Melting is closed uniformly
The female ingot of gold is put in the foraminate quartz test tube of bottom belt after cutting into alloy block, treats that stove internal gas pressure reduces to 10-3 Below Pa, fills
Enter a certain amount of argon, by copper induction coil the alloy block in quartz test tube quickly heated and be allowed to melt, after alloy melting
Heating 1.5 minutes, pressing spray to cast valve under the air pressure of 0.06 ~ 0.08 MPa by alloy melt spray to cast to rotating speed is 1500 revs/min
On the copper roller of clock, strip can be formed.
(4) gained copper nickel-phosphorus alloy strip is placed in 50 DEG C, in the ferric chloride solution of 3.5mol/L, freely corrodes 5 little
Time.Utilize dehydrated alcohol, deionized water to carry out ultrasonic waves for cleaning in gained powder subsequently, utilize high speed centrifuge to carry out thing and divide mutually
From, centrifuge speed is set as 8000 revs/min, is placed in by gained powder in the drying baker of 60 DEG C 2.5 hours, obtains Ni5P2Powder
End.Ni5P2Powder has photocatalytic degradation effect to Congo red, is added into Congo red organic dye solution, solution concentration
It is chosen to be 1 × 10-5Mol/L, is placed in camera bellows after ultrasonic 30min, reaches adsorption-desorption balance, uses uviol lamp as light source
Carry out Degrading experiment.It is found by experiment that, the Ni after 90min, prepared by the present embodiment5P2Powder can to the degradation rate of Congo red
Reach more than 96%；Under same light catalytic condition, improve 6.22-9.10% than the degradation rate of the nickel phosphide of other patterns.
Embodiment 3
(1) weigh by industrial pure copper 14.5%, industrial pure ni 29.25%, the mass percent of copper phosphorus intermediate alloy 56.25%
Raw material.Wherein in copper phosphorus intermediate alloy, the mass percent of copper is 92.0%, and the mass percent of phosphorus is 8.0%.
(2) in vacuum arc melting furnace, copper nickel-phosphorus alloy ingot is founded.Specifically comprise the following steps that and the raw material prepared is put
In the copper crucible of electric arc furnace, utilize the high-temperature electric arc heating melt raw material that tungsten electrode head and the electric discharge of alloy mother's ingot are formed, repeatedly melt
Refining obtains female ingot.Here, melt back 5 times is uniform to ensure melting.Every time before melting, striking, will be by copper nickel-phosphorus alloy
The oxide skin of female ingot surface polishes off, and has ensured that striking is abundant, melting is uniform.
(3) gained copper nickel-phosphorus alloy mother's ingot carry out fine vacuum melt spinning method process make strip.Melting is closed uniformly
The female ingot of gold is put in the foraminate quartz test tube of bottom belt after cutting into alloy block, treats that stove internal gas pressure reduces to 10-3 Below Pa, fills
Enter a certain amount of argon, by copper induction coil the alloy block in quartz test tube quickly heated and be allowed to melt, after alloy melting
Heating 2 minutes, pressing spray to cast valve under the air pressure of 0.06 ~ 0.08 MPa by alloy melt spray to cast to rotating speed is 1800 revs/min
Copper roller on, strip can be formed.
(4) gained copper nickel-phosphorus alloy strip is placed in 80 DEG C, in the ferric chloride solution of 4.5mol/L, freely corrodes 2 little
Time.Utilize dehydrated alcohol, deionized water to carry out ultrasonic waves for cleaning in gained powder subsequently, utilize high speed centrifuge to carry out thing and divide mutually
From, centrifuge speed is set as 12000 revs/min, is placed in by gained powder in the drying baker of 80 DEG C 1.5 hours, obtains Ni5P2
Powder.The present embodiment Congo red is had photocatalytic degradation effect, be added into Congo red organic dye solution, solution
Concentration is chosen to be 1 × 10-5Mol/L, is placed in camera bellows after ultrasonic 30min, reaches adsorption-desorption balance, uses uviol lamp conduct
Light source carries out Degrading experiment.It is found by experiment that, the Ni after 90min, prepared by the present embodiment5P2The powder degraded to Congo red
Rate can reach more than 95.7%；Under same light catalytic condition, improve 5.90-than the degradation rate of the nickel phosphide of other patterns
8.75%。
Claims (7)
1. a porous Ni P based compound, the mol ratio of Ni Yu P is 2-2.7:1；Being a kind of spongy particles, particle diameter is 10-
50 μm, aperture is 0.6-3.5 μm.
2. the preparation method of porous Ni P based compound described in a claim 1, it is characterised in that comprise the following steps:
(1) using copper phosphorus intermediate alloy as phosphorus source, copper-nickel intermediate alloy or industrial pure ni as nickel source, vacuum arc is used to melt
Furnace carries out melting, forms metal mother's ingot；Copper, the mol ratio of nickel are 2.18-5.90:1；
(2) utilize high vacuum single roller to revolve system of quenching and strip is quenched in the rotation of metal mother's ingot；
(3) being placed in ferric chloride solution by strip and carry out corrosion treatmentCorrosion Science, gained powder is Ni P based compound；Ferric chloride solution
Concentration be 1.5 4.5mol/L, etching time is 1 10 hours, and corrosion temperature scope is 25 DEG C 95 DEG C.
Preparation method the most according to claim 2, it is characterised in that copper phosphorus intermediate alloy used, the percent mass of its component
Ratio is: phosphorus 6.0 15.0%, and surplus is copper.
4. according to preparation method described in Claims 2 or 3, it is characterised in that copper nickel intermediate alloy used, the quality of its component
Percentage ratio is: nickel 30.0 50.0%, and surplus is copper.
Preparation method the most according to claim 4, it is characterised in that alloy mother's ingot uses vacuum arc melting furnace melt back
25 times.
Preparation method the most according to claim 5, it is characterised in that step 2 sets single roller range of speeds as 1,000 2500
Rev/min.
Preparation method the most according to claim 6, it is characterised in that use distilled water, dehydrated alcohol to step 3 gained powder
Carry out ultrasonic waves for cleaning 37 times, centrifugal 35 times, dried 13 hours；Centrifugal rotational speed is 6,000 15000 revs/min；Dry
Dry temperature is 25 DEG C 90 DEG C.
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| CN107744829A (en) * | 2017-11-17 | 2018-03-02 | 福州大学 | A kind of preparation of metal phosphide catalyst and its application in hydrogenation deoxidation catalytic reaction |
| CN109731589A (en) * | 2019-01-26 | 2019-05-10 | 南京理工大学 | The method that circulation in situ improves NiP amorphous alloy catalytic performance |
| CN113549782A (en) * | 2021-08-03 | 2021-10-26 | 苏州昆腾威新材料科技有限公司 | Nickel-phosphorus intermediate alloy and preparation method and application thereof |
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| CN113549782B (en) * | 2021-08-03 | 2022-02-11 | 苏州昆腾威新材料科技有限公司 | Nickel-phosphorus intermediate alloy and preparation method and application thereof |
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