CN114870850B - Fe-Ni-Ce catalyst alloy powder and preparation method and application thereof - Google Patents
Fe-Ni-Ce catalyst alloy powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 60
- 239000000956 alloy Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 32
- 239000010432 diamond Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 239000006258 conductive agent Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 241000080590 Niso Species 0.000 claims description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- 239000007868 Raney catalyst Substances 0.000 claims description 11
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004327 boric acid Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 230000003068 static effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 229910002555 FeNi Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000007777 multifunctional material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
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- 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
- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/065—Composition of the material produced
- B01J2203/0655—Diamond
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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
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Abstract
The invention discloses Fe-Ni-Ce catalyst alloy powder, a preparation method and application thereof, wherein the preparation method of the Fe-Ni-Ce catalyst alloy powder comprises the following steps: (1) pretreatment of an electrode; (2) Preparing an electrolytic aqueous solution comprising ferric salt, nickel salt, cerium salt, boric acid, a conductive agent and a complexing agent; (3) And preparing Fe-Ni-Ce catalyst alloy powder by ultrasonic-assisted electrodeposition. The Fe-Ni-Ce catalyst alloy powder prepared by the method has fine particle size, dendritic development and larger specific surface area, and can increase the contact area of graphite and Fe-Ni-Ce catalyst alloy powder, thereby improving the catalytic performance of the catalyst powder. The ultrasonic-assisted electrodeposition preparation method has the advantages of simple flow, simple and convenient operation, low cost, large-scale production and the like, can be used in the artificial diamond production process, and has remarkable practical value and economic value.
Description
Technical Field
The invention relates to a method for preparing Fe-Ni-Ce catalyst alloy powder for diamond by ultrasonic electrodeposition, and a preparation method and application thereof, belonging to the technical field of catalyst materials used in the artificial diamond production process.
Background
The diamond is a superhard multifunctional material, has excellent physicochemical characteristics of higher hardness and heat conductivity, wider light transmission wave band, radiation resistance, strong acid and alkali corrosion resistance and the like, and has great application potential in high-tech fields such as electronic devices, national defense, communication, aerospace and the like. (see: sun Shiyang, late medium wave, xu Pingping, et Al. First principles of formation of diamond (111)/Al interface and performance. J. Programmes of physics, 2021,70 (18): 188101.) diamond has been industrialized for over half a century since the first successful synthesis of diamond by G.E. company by the static high temperature high pressure method using a metal catalyst and graphite. The synthetic method of artificial diamond mainly uses high-temperature high-pressure catalyst method, and catalyst material is an indispensable material for synthesizing artificial diamond, and mainly has the function of reducing synthetic temperature and pressure. At present, fe-Ni based catalyst powder is generally adopted for synthesizing the artificial diamond.
Generally, the catalyst and graphite contain O, S, P and other impurity elements, and these elements can form stable compounds with certain metal elements in the catalyst under high temperature and high pressure conditions, so that the supply of carbon sources is blocked, the nucleation and growth of diamond are affected, the catalytic activity of the catalyst is reduced, or defects such as inclusion are formed in the diamond, and the crystal quality of the diamond is affected.
Rare earth is composed of lanthanoid elements and yttrium and scandium elements closely related to lanthanoid elements in the periodic table. The rare earth element is in the third subgroup, the atomic radius is large (173.5 pm-187.0 pm), the outer layer 2 s electrons and the secondary outer layer 5d are extremely easy to lose 1 The electrons or the 4f layer 1 electrons become 3-valence ions, so the catalyst has strong oxygen affinity, and rare earth can be added as deoxidizing and desulfurizing agents, thereby improving the synthesis quality of the diamond. Document "Dai Lanfang, wang Shao, tang Zhongjie use of rare earths in synthetic diamond catalysts [ J]Rare earth, 2005,26 (3): 79-81, "reports a method for synthesizing diamond by adopting NiFe alloy powder doped with a small amount of rare earth as a raw material under the conditions of ultrahigh pressure and high temperature through a certain technological process. The method obviously improves the coarse grain percentage, the static pressure strength and the impact toughness of the diamond and improves the high-temperature toughness, however, rare earth and NiFe alloy powder are easy to mix unevenly, and the quality of the synthesized diamond is affected. Effect of rare earths on powder catalyst synthesis of diamond [ J ]]The diamond and abrasive grinding tool engineering 2009, 37-42 report a method for preparing catalyst powder by using FeNi powder and rare earth additive as raw materials and adopting vacuum/inert gas atomization technology. The catalyst powder obtained by the method is beneficial to improving the mixing unit yield of diamond, the proportion of coarse particles, the static pressure intensity, the impact toughness value and reducing the magnetic susceptibility. However, the production cost of the method is high, and in the preparation process, the alloy liquid is contacted with the refractory material, so that non-metallic inclusion is difficult to avoid being brought in.
The powder catalysts currently on the market are mainly prepared by a rapid solidification and atomization method, including inert gas atomization and high-pressure water atomization methods. The catalyst powder prepared by the inert gas atomization method has the advantages of high sphericity and low oxygen content, but has high cost, and the inert gas needs to be built into a recovery device; the high-pressure water atomization method has the advantages of low investment and low cost, but the iron-based catalyst powder is easy to cause high oxygen content in powder in the processes of smelting under the atmosphere, water atomization preparation, powder storage and the like, and the quality of the artificial diamond is influenced. Therefore, the preparation method of the catalyst powder with low cost, high efficiency, simple method, uniform particle size, high purity and easy industrialization is urgently needed to be developed.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide Fe-Ni-Ce catalyst alloy powder for synthesizing artificial diamond, which has less impurity, smaller powder particle diameter, developed dendrite shape and larger specific surface area; the second object of the invention is to provide a preparation method of the catalyst alloy powder, which is simple to operate and low in cost; the third object of the invention is to provide the application of the Fe-Ni-Ce catalyst alloy powder in the preparation of artificial diamond.
The technical scheme is as follows: the Fe-Ni-Ce catalyst alloy powder is electrolyte containing ferric salt, nickel salt, cerium salt, a conductive agent and a complexing agent, and is prepared by an ultrasonic-assisted electrodeposition process. The Fe-Ni-Ce catalyst alloy powder comprises the following components in percentage by mass: 30-79% of Fe, 20-70% of Ni and 1-50% of Ce.
Preferably, the Fe-Ni-Ce catalyst alloy powder comprises the following components in percentage by mass: 60-79% of Fe, 20-50% of Ni and 1-20% of Ce.
The preparation method of the Fe-Ni-Ce catalyst alloy powder comprises the following steps:
(1) Pretreatment of a conductive substrate: cutting a conductive matrix material into small rectangular pieces, ultrasonically cleaning the cut conductive matrix material in absolute ethyl alcohol, washing with deionized water, ultrasonically cleaning in dilute hydrochloric acid, cleaning with deionized water, and drying for later use;
(2) Preparing an electrolytic aqueous solution: the electrolytic aqueous solution comprises ferric salt, nickel salt, cerium salt, boric acid, a conductive agent and a complexing agent;
(3) Preparing Fe-Ni-Ce catalyst alloy powder by ultrasonic-assisted electrodeposition: adopting a constant-current double-anode single-cathode system, taking the conductive substrate treated in the step (1) as a cathode, taking a nickel plate and an iron plate as anodes, ultrasonically assisting the electrolytic aqueous solution prepared in the step (2), centrifuging the electrolytic aqueous solution after the ultrasonic assisted electrodeposition is finished, vacuum-filtering, washing with alcohol, and vacuum-drying to obtain Fe-Ni-Ce catalyst alloy powder.
Preferably, in step (1), the conductive base material is nickel mesh, raney nickel or iron mesh.
Preferably, in the step (2), the iron salt is one or a mixture of several of water-soluble iron salts.
Preferably, in the step (2), the nickel salt is one or a mixture of several of water-soluble nickel salts.
Preferably, in the step (2), the cerium salt is one or a mixture of several water-soluble cerium salts.
Preferably, in step (2), the conductive agent comprises an alkali metal inorganic salt and/or a soluble ammonium salt.
Preferably, in the step (2), the complexing agent is one or a mixture of several water-soluble citrates.
Preferably, in the step (2), the concentration of the ferric salt in the electrolytic aqueous solution is 20-50 g/L, the concentration of the nickel salt is 40-60 g/L, the concentration of the cerium salt is 1-30 g/L, the concentration of the conductive agent is 50-90 g/L, the concentration of the complexing agent is 50-100 g/L, and the concentration of the boric acid is 20-50 g/L.
Preferably, in step (2), the pH of the aqueous electrolytic solution is 3 to 7.
Preferably, in the step (3), the temperature of the electrolytic aqueous solution at the time of ultrasonic-assisted electrodeposition is 30-80 ℃ and the current density is 0.5-3.0A/cm 2 The frequency of the ultrasonic wave is 20-100kHz.
Preferably, in the step (3), the time of ultrasonic-assisted electrodeposition is 5 to 20 minutes.
The invention also comprises the application of the Fe-Ni-Ce catalyst alloy powder in preparing diamond.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The Fe-Ni-Ce catalyst alloy powder prepared by the method has fine particle size, dendritic development and larger specific surface area, and can increase the contact area of graphite and Fe-Ni-Ce catalyst alloy powder, thereby improving the catalytic performance of the catalyst powder;
(2) The invention adopts the ultrasonic-assisted electrodeposition preparation method, has the advantages of simple flow, simple and convenient operation, low cost, easy industrialization and the like, and has better social and economic benefits;
(3) The artificial diamond synthesized by the Fe-Ni-Ce catalyst alloy powder provided by the invention has the advantages of large grain size, good crystal color, few defects, higher static pressure intensity and good thermal shock intensity.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing alloy powder by ultrasonic electrodeposition;
FIG. 2 is an SEM image of Fe-Ni-Ce catalyst alloy powder.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
(1) Pretreatment of nickel screen
Cutting into 2cm×2cm nickel net, and ultrasonic cleaning in absolute ethanol for 10min; washing with deionized water, soaking foam nickel in dilute hydrochloric acid, and ultrasonically cleaning for 10min; and then washing with deionized water, and drying for later use.
(2) Preparing electrolytic aqueous solution
Weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 5 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing NiSO 60g/L 4 ·6H 2 O、20g/L FeSO 4 ·7H 2 O、22g/L Ce 2 (SO 4 ) 3 、60g/L NH 4 Cl, 50g/L sodium citrate, 35g/L H 3 BO 3 。
(3) Fe-Ni-Ce catalyst alloy powder prepared by ultrasonic-assisted electrodeposition
Adopting a constant-current double-anode single-cathode system, taking the nickel screen pretreated in the step (1) as a cathode, and taking a nickel plate and an iron plate as anodes. Preparation of alloy powder by ultrasonic electrodepositionThe device is schematically shown in figure 1. FIG. 1 is a schematic diagram of an apparatus for preparing alloy powder by ultrasonic electrodeposition; wherein the power supply 1 comprises an output voltage display window 2, a voltage adjustment button 3, an output current display window 4 and a current adjustment button 5. The negative electrode of the power supply 1 is connected with the nickel screen cathode 7, and the positive electrode of the power supply 1 is respectively connected with the iron plate anode 6 and the nickel plate anode 8. The nickel screen cathode 7, the iron plate anode 6 and the nickel plate anode 8 are inserted into the plating tank 9, the electrolytic tank 9 is filled with the electrolytic aqueous solution 10, and the entire electrolytic apparatus is placed into the ultrasonic tank 11. In the ultrasonic assisted electrodeposition, the temperature of the heated electrolytic aqueous solution was 50℃and the current density was controlled to 1.0A/cm by adjusting the current adjusting button 5 2 . The time of ultrasonic assisted electrodeposition was 15min and the ultrasonic frequency was 40kHz. After ultrasonic assisted electrodeposition, carrying out high-speed centrifugation, vacuum suction filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain Fe-Ni-Ce catalyst alloy powder.
The morphology analysis of the Fe-Ni-Ce catalyst alloy powder obtained by the preparation is carried out by adopting a ZEISS EVO18 scanning electron microscope of Karl ZEISS company, germany, and the result is shown in figure 2. FIG. 2 is an SEM image of Fe-Ni-Ce catalyst alloy powder, and as can be seen from FIG. 2, the Fe-Ni-Ce catalyst alloy powder exhibits dendritic morphology. This is because during electroplating, ions are reduced to nuclei at the cathode and grow in the direction of the most abundant ion source. The ion concentration in the solution increases from the cathode to the center of the solution, so that the growth direction grows rapidly towards the periphery far from the cathode. The powder is separated from the nickel screen with the aid of ultrasound. The weight percentage of the Fe-Ni-Ce catalyst alloy powder measured by ICP-OES inductively coupled plasma spectrum 2100DV is as follows: 75% Fe,18% Ni,7% Ce.
Example 2
(1) Pretreatment of Raney nickel
Cutting Raney nickel into 2cm multiplied by 2cm, and placing the Raney nickel into absolute ethyl alcohol for ultrasonic cleaning for 10min; washing with deionized water, soaking foam nickel in dilute hydrochloric acid, and ultrasonically cleaning for 10min; and then washing with deionized water, and drying for later use.
(2) Preparing electrolytic aqueous solution
Weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 40g/L NiSO 4 ·6H 2 O、20g/L FeSO 4 ·7H 2 O、15g/L Ce 2 (SO 4 ) 3 、50g/L NH 4 Cl, 70g/L sodium citrate, 30g/L H 3 BO 3 。
(3) Fe-Ni-Ce catalyst alloy powder prepared by ultrasonic-assisted electrodeposition
Step (3) in example 1 is different in that: the temperature of the electrolytic aqueous solution during ultrasonic-assisted electrodeposition is 60 ℃; the current density was 2.0A/cm 2 The time of ultrasonic assisted electrodeposition was 10min and the ultrasonic frequency was 60kHz. After the ultrasonic assisted electrodeposition is finished, the dendritic fine Fe-Ni-Ce catalyst alloy powder can be obtained on the cathode. After the ultrasonic assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum suction filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain Fe-Ni-Ce catalyst alloy powder. The weight percentage of the Fe-Ni-Ce catalyst alloy powder measured by ICP-OES inductively coupled plasma spectrum 2100DV is as follows: 70% of Fe,22% of Ni and 8% of Ce.
Example 3
(1) Pretreatment of Raney nickel
Cutting Raney nickel into 2cm multiplied by 2cm, and placing the Raney nickel into absolute ethyl alcohol for ultrasonic cleaning for 10min; washing with deionized water, soaking foam nickel in dilute hydrochloric acid, and ultrasonically cleaning for 10min; and then washing with deionized water, and drying for later use.
(2) Preparing electrolytic aqueous solution
Weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 40g/L NiSO 4 ·6H 2 O、30g/L FeSO 4 ·7H 2 O、30g/L Ce 2 (SO 4 ) 3 、70g/L NH 4 Cl, 80g/L sodium citrate, 40g/L H 3 BO 3 。
(3) Fe-Ni-Ce catalyst alloy powder prepared by ultrasonic-assisted electrodeposition
Step (2) in example 1 is different in that: the temperature of the electrolytic aqueous solution during ultrasonic-assisted electrodeposition is 40 ℃; the current density was 1.5A/cm 2 The time of ultrasonic assisted electrodeposition was 10min and the ultrasonic frequency was 80kHz. And after the ultrasonic auxiliary electrodeposition is finished, dendritic Fe-Ni-Ce catalyst alloy powder can be obtained on the cathode. After the ultrasonic assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum suction filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain Fe-Ni-Ce catalyst alloy powder. The weight percentage of the Fe-Ni-Ce catalyst alloy powder measured by ICP-OES inductively coupled plasma spectrum 2100DV is as follows: 73% Fe,18% Ni,9% Ce.
Example 4
(1) Pretreatment of iron net
Placing the iron net cut into 2cm multiplied by 2cm in absolute ethyl alcohol for ultrasonic cleaning for 10min; washing with deionized water, soaking foam nickel in dilute hydrochloric acid, and ultrasonically cleaning for 10min; and then washing with deionized water, and drying for later use.
(2) Preparing electrolytic aqueous solution
Weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 4 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing NiSO 60g/L 4 ·6H 2 O、50g/L FeSO 4 ·7H 2 O、1g/L Ce 2 (SO 4 ) 3 、90g/L NH 4 Cl, 100g/L sodium citrate, 50g/L H 3 BO 3 。
(3) Fe-Ni-Ce catalyst alloy powder prepared by ultrasonic-assisted electrodeposition
Step (2) in example 1 is different in that: the temperature of the electrolytic aqueous solution during ultrasonic-assisted electrodeposition is 30 ℃; the current density was 3A/cm 2 Super-therapeutic deviceThe time of the acoustic assisted electrodeposition was 5min and the ultrasonic frequency was 100kHz. And after the ultrasonic auxiliary electrodeposition is finished, dendritic Fe-Ni-Ce catalyst alloy powder can be obtained on the cathode. After the ultrasonic assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum suction filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain Fe-Ni-Ce catalyst alloy powder. The weight percentage of the Fe-Ni-Ce catalyst alloy powder measured by ICP-OES inductively coupled plasma spectrum 2100DV is as follows: 69% Fe,25% Ni,6% Ce.
Example 5
The Fe-Ni-Ce catalyst alloy powder prepared in the examples 1-4 and the commercial FeNi catalyst alloy powder are respectively and uniformly mixed with graphite powder according to the ratio of 4:6, and are pressed into a cavity synthetic column with the diameter of 39 mm. Diamond synthesis was performed using a cavity of phi 39mm at a pressure of 5.2GPa, a temperature above 1450 ℃ and a heating time of about 20min, and the resultant diamond was tested for hydrostatic strength, TI, TTI performance, and the results are shown in table 1.
TABLE 1 main performance index of Fe-Ni-Ce catalyst alloy powder for diamond synthesis
As can be seen from Table 1, compared with the commercial FeNi catalyst powder, the Fe-Ni-Ce catalyst alloy powder prepared in the examples 1-4 provided by the invention can effectively increase the mixing unit yield, and simultaneously improve the impact toughness TI value and the thermal impact toughness TTI value of the synthetic diamond, and increase the static pressure strength, thereby indicating that the Fe-Ni-Ce catalyst alloy powder has good market application prospect.
Claims (2)
1. The Fe-Ni-Ce catalyst alloy powder for preparing the artificial diamond is characterized in that the Fe-Ni-Ce catalyst alloy powder is electrolyte containing ferric salt, nickel salt, cerium salt, a conductive agent and a complexing agent, and is prepared by an ultrasonic auxiliary electrodeposition process; the Fe-Ni-Ce catalyst alloy powder comprises the following components in percentage by mass: 70% of Fe,22% of Ni and 8% of Ce, and the preparation method of the Fe-Ni-Ce catalyst alloy powder comprises the following steps of:
(1) Pretreatment of a conductive substrate: cutting Raney nickel as a conductive matrix material into 2cm multiplied by 2cm small rectangular pieces, ultrasonically cleaning the cut conductive matrix material in absolute ethyl alcohol for 10min, washing with deionized water, ultrasonically cleaning in dilute hydrochloric acid for 10min, washing with deionized water, and drying for later use;
(2) Preparing an electrolytic aqueous solution:
weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 40g/L NiSO 4 ·6H 2 O、20g/L FeSO 4 ·7H 2 O、15g/L Ce 2 (SO 4 ) 3 、50g/L NH 4 Cl, 70g/L sodium citrate, 30g/L H 3 BO 3 ；
(3) Preparing Fe-Ni-Ce catalyst alloy powder by ultrasonic-assisted electrodeposition: adopting a constant-current double-anode single-cathode system, taking Raney nickel treated in the step (1) as a cathode, taking a nickel plate and an iron plate as anodes, and ultrasonically assisting the electrolytic aqueous solution prepared in the step (2) to be electrodeposited, wherein the temperature of the electrolytic aqueous solution is 60 ℃ during the ultrasonic assisting process; the current density was 2.0A/cm 2 The time of ultrasonic auxiliary electrodeposition is 10min, and the ultrasonic frequency is 60kHz; after the ultrasonic-assisted electrodeposition is finished, carrying out centrifugal separation, vacuum suction filtration and alcohol washing on the electrolytic aqueous solution, and carrying out vacuum drying to obtain Fe-Ni-Ce catalyst alloy powder.
2. A method for preparing the Fe-Ni-Ce catalyst alloy powder for preparing the artificial diamond according to claim 1, comprising the following steps:
(1) Pretreatment of a conductive substrate: cutting Raney nickel as a conductive matrix material into 2cm multiplied by 2cm small rectangular pieces, ultrasonically cleaning the cut conductive matrix material in absolute ethyl alcohol for 10min, washing with deionized water, ultrasonically cleaning in dilute hydrochloric acid for 10min, washing with deionized water, and drying for later use;
(2) Preparing an electrolytic aqueous solution:
weighing NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、Ce 2 (SO 4 ) 3 、NH 4 Cl, sodium citrate, H 3 BO 3 Adding into deionized water, stirring thoroughly to dissolve, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 40g/L NiSO 4 ·6H 2 O、20g/L FeSO 4 ·7H 2 O、15g/L Ce 2 (SO 4 ) 3 、50g/L NH 4 Cl, 70g/L sodium citrate, 30g/L H 3 BO 3 ；
(3) Preparing Fe-Ni-Ce catalyst alloy powder by ultrasonic-assisted electrodeposition: adopting a constant-current double-anode single-cathode system, taking Raney nickel treated in the step (1) as a cathode, taking a nickel plate and an iron plate as anodes, and ultrasonically assisting the electrolytic aqueous solution prepared in the step (2) to be electrodeposited, wherein the temperature of the electrolytic aqueous solution is 60 ℃ during the ultrasonic assisting process; the current density was 2.0A/cm 2 The time of ultrasonic auxiliary electrodeposition is 10min, and the ultrasonic frequency is 60kHz; after the ultrasonic-assisted electrodeposition is finished, carrying out centrifugal separation, vacuum suction filtration and alcohol washing on the electrolytic aqueous solution, and carrying out vacuum drying to obtain Fe-Ni-Ce catalyst alloy powder.
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