CN114870850A - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000000843 powder Substances 0.000 title claims abstract description 74
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 59
- 239000000956 alloy Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 239000010432 diamond Substances 0.000 claims abstract description 31
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- 238000000034 method Methods 0.000 claims abstract description 27
- 150000000703 Cerium Chemical class 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004327 boric acid Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 13
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- 229910052742 iron Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 8
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 4
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- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- 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 description 8
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- 229910002555 FeNi Inorganic materials 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000007712 rapid solidification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 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
- 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
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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
-
- 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
-
- 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
Abstract
The invention discloses Fe-Ni-Ce catalyst alloy powder and a preparation method and application thereof, wherein the preparation method of the Fe-Ni-Ce catalyst alloy powder comprises the following steps: (1) pretreating the 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 the advantages of fine particle size, developed dendrite shape and larger specific surface area, and can increase the contact area of graphite and the Fe-Ni-Ce catalyst alloy powder so as to improve the catalytic performance of the catalyst powder. The ultrasonic-assisted electrodeposition preparation method adopted by the invention has the advantages of simple flow, simple and convenient operation, low cost, large-scale production and the like, can be used in the production process of the artificial diamond, and has obvious 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, a preparation method and application thereof, belonging to the technical field of catalyst materials used in the production process of artificial diamond.
Background
The diamond is a superhard multifunctional material, has excellent physicochemical characteristics such as higher hardness and thermal 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. (Sun Shiyang, late-mid-wave, gentle leveling, etc.. first principles research on formation and performance of diamond (111)/Al interface [ J ]. Physics, 2021,70(18):188101.) since G.E. company successfully synthesized diamond by using metal catalyst and graphite for the first time through static high-temperature high-pressure method, the industrial production of diamond has been already known for over half a century. The synthesis of artificial diamond is mainly based on high-temperature high-pressure catalyst method, and the catalyst material is indispensable material in the synthesis of artificial diamond, and mainly plays a role in reducing synthesis temperature and pressure. At present, the synthesis of artificial diamond is generally carried out by adopting Fe-Ni-based catalyst powder.
Generally, the catalyst and graphite contain impurity elements such as O, S, P, which form stable compounds with some metal elements in the catalyst under high temperature and high pressure conditions, hinder the supply of carbon source, affect the nucleation and growth of diamond, reduce the catalytic activity of the catalyst or form defects such as inclusions in diamond, and thus affect the crystal quality of diamond.
Rare earth is composed of lanthanide element in the periodic table of chemical elements and yttrium and scandium closely related to lanthanide. The rare earth elements are positioned in a third subgroup, have large atomic radius (173.5 pm-187.0 pm), and easily lose 2 s electrons of the outer layer and the secondary outer layer 5d 1 The single electron or 1 electron of the 4f layer becomes 3-valent ions, so that the catalyst has strong oxygen affinity, and rare earth can be added into the catalyst to serve as a deoxidizing agent and a desulfurizing agent, so that the synthesis quality of the diamond is improved. The application of rare earth in artificial diamond catalyst is 'Dailanfan, Wangshoubin, Dongzhongjie' in literature [ J]Rare earth, 2005,26(3):79-81 "reports a method for synthesizing diamond by using NiFe alloy powder doped with a small amount of rare earth as a raw material and through a certain process flow under the conditions of ultrahigh pressure and high temperature. 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, but the rare earth and the NiFe alloy powder are easy to mix unevenly, thereby influencing the quality of the synthesized diamond. Document "role of rare earths in synthesis of diamond by powder catalyst]Diamond and abrasive tool engineering, 2009, (6):37-42, "reports 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 methodIs favorable for improving the mixed unit yield of the diamond, the coarse particle proportion, the static pressure strength and the impact toughness value and reducing the magnetic susceptibility. However, the method has high production cost, and in the preparation process, the alloy liquid is contacted with the refractory material, so that the non-metallic inclusions are difficult to avoid being brought in.
The powder catalyst on the market is mainly prepared by a rapid solidification atomization method, including an inert gas atomization method and a high-pressure water atomization method. The catalyst powder prepared by the inert gas atomization method has the advantages of high sphericity degree and low oxygen content, but the cost is high, and a recovery device is required to be built for the inert gas; the high-pressure water atomization method has less investment and low cost, but the iron-based catalyst powder is easy to cause high oxygen content in the powder in the processes of smelting in the atmosphere, water atomization preparation, powder storage and the like, and the quality of the artificial diamond is influenced. Therefore, there is an urgent need to develop a method for preparing catalyst powder which is low in cost, high in efficiency, simple in method, uniform in particle size, high in purity and easy to industrialize.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide Fe-Ni-Ce catalyst alloy powder for synthesizing artificial diamond, which has less impurities, smaller powder particle size, developed dendrite shape and larger specific surface area; the second purpose 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 purpose of the invention is to provide the application of the Fe-Ni-Ce catalyst alloy powder in preparing the artificial diamond.
The technical scheme is as follows: the Fe-Ni-Ce catalyst alloy powder is prepared from an electrolyte containing iron salt, nickel salt, cerium salt, a conductive agent and a complexing agent 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 the conductive substrate: cutting the conductive base material into small rectangular pieces, ultrasonically cleaning the cut conductive base material in absolute ethyl alcohol, washing the conductive base material with deionized water, ultrasonically cleaning the conductive base material in dilute hydrochloric acid, cleaning the conductive base material with deionized water, and drying the conductive base material for later use;
(2) preparing an electrolytic aqueous solution: the electrolytic water solution comprises iron 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: and (2) 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 an anode, ultrasonically assisting the electrolytic aqueous solution prepared in the step (2) for electrodeposition, and after the ultrasonic-assisted electrodeposition is finished, carrying out centrifugal separation, vacuum filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain the Fe-Ni-Ce catalyst alloy powder.
Preferably, in the step (1), the conductive base material is a nickel mesh, raney nickel or iron mesh.
Preferably, in the step (2), the iron salt is one or a mixture of several water-soluble iron salts.
Preferably, in the step (2), the nickel salt is one or a mixture of water-soluble nickel salts.
Preferably, in the step (2), the cerium salt is one or a mixture of several of water-soluble cerium salts.
Preferably, in the step (2), the conductive agent includes 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 of water-soluble citrate.
Preferably, in the step (2), the concentration of the iron 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 the step (2), the pH value of the electrolytic aqueous solution is 3 to 7.
Preferably, in the step (3), the temperature of the electrolytic aqueous solution during the ultrasonic-assisted electrodeposition is 30-80 ℃, and the current density is 0.5-3.0A/cm 2 Ultrasonic wave, and a method of producing the sameThe frequency of (2) is 20-100 kHz.
Preferably, in the step (3), the time of ultrasonic-assisted electrodeposition is 5-20 min.
The invention also comprises the application of the Fe-Ni-Ce catalyst alloy powder in preparing diamond.
Has the advantages 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 the advantages of fine particle size, developed dendrite shape and larger specific surface area, and can increase the contact area of graphite and the Fe-Ni-Ce catalyst alloy powder so as to improve the catalytic performance of the catalyst powder;
(2) the preparation method of ultrasonic-assisted electrodeposition 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 large grain particles, good crystal color, few defects, higher static pressure strength and good thermal shock strength.
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 explained by combining the attached drawings.
Example 1
(1) Pretreatment of nickel screen
Placing the nickel screen cut into 2cm multiplied by 2cm into absolute ethyl alcohol for ultrasonic cleaning for 10 min; washing with deionized water, soaking foamed nickel in dilute hydrochloric acid, and ultrasonic cleaning for 10 min; and then washing the mixture by using deionized water, and drying the mixture 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, and chargingStirring until completely dissolved, adjusting pH to 5 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 60g/L NiSO 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) Ultrasonic-assisted electrodeposition for preparing Fe-Ni-Ce catalyst alloy powder
Adopting a constant current double-anode single-cathode system, taking the nickel net pretreated in the step (1) as a cathode, and taking a nickel plate and an iron plate as an anode. The schematic diagram of the device for preparing the alloy powder by ultrasonic electrodeposition is 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 adjusting button 3, an output current display window 4 and a current adjusting button 5. The negative pole of the power supply 1 is linked with the nickel screen cathode 7, and the positive pole of the power supply 1 is linked with the iron plate anode 6 and the nickel plate anode 8 respectively. The nickel screen cathode 7, the iron plate anode 6 and the nickel plate anode 8 are inserted into an electroplating bath 9, an electrolytic water solution 10 is filled in the electrolytic bath 9, and the whole electrolytic device is placed in an ultrasonic wave groove 11. When the ultrasonic-assisted electrodeposition is carried out, the temperature of the electrolytic aqueous solution is heated to 50 ℃, and the current density is controlled to be 1.0A/cm by adjusting the current adjusting button 5 2 . The time of ultrasonic-assisted electrodeposition is 15min, and the ultrasonic frequency is 40 kHz. After ultrasonic-assisted electrodeposition, carrying out high-speed centrifugation, vacuum filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain Fe-Ni-Ce catalyst alloy powder.
The morphology of the prepared Fe-Ni-Ce catalyst alloy powder was analyzed by using a ZEISS EVO18 scanning electron microscope (Karl Zeiss Co., Germany), and the result is shown in FIG. 2. FIG. 2 is an SEM image of Fe-Ni-Ce catalyst alloy powder, and it can be seen from FIG. 2 that Fe-Ni-Ce catalyst alloy powder exhibits a dendritic morphology. This is because during electroplating, ions are reductively nucleated at the cathode and grow toward the richest direction of the ion source. The ion concentration in the solution is increased from the cathode to the center of the solution, so that the growth direction grows rapidly towards the periphery far away from the cathode. The powder was detached from the nickel mesh with the aid of ultrasound. The weight percentage of the Fe-Ni-Ce catalyst alloy powder is determined by ICP-OES inductively coupled plasma spectroscopy 2100DV as follows: 75% of Fe, 18% of Ni and 7% of Ce.
Example 2
(1) Pretreatment of Raney nickel
Putting Raney nickel cut into 2cm multiplied by 2cm into absolute ethyl alcohol for ultrasonic cleaning for 10 min; washing with deionized water, soaking foamed nickel in dilute hydrochloric acid, and ultrasonic cleaning for 10 min; and then washing the mixture by using deionized water, and drying the mixture 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 until completely dissolved, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing NiSO 40g/L 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) Ultrasonic-assisted electrodeposition for preparing Fe-Ni-Ce catalyst alloy powder
The difference from step (3) in example 1 is that: the temperature of the electrolytic aqueous solution is 60 ℃ during ultrasonic-assisted electrodeposition; the current density is 2.0A/cm 2 The time of ultrasonic-assisted electrodeposition is 10min, and the ultrasonic frequency is 60 kHz. And obtaining the dendritic superfine Fe-Ni-Ce catalyst alloy powder on the cathode after the ultrasonic-assisted electrodeposition is finished. And after the ultrasonic-assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum 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 is determined by ICP-OES inductively coupled plasma spectroscopy 2100DV as follows: 70% of Fe, 22% of Ni and 8% of Ce.
Example 3
(1) Pretreatment of Raney nickel
Putting Raney nickel cut into 2cm multiplied by 2cm into absolute ethyl alcohol for ultrasonic cleaning for 10 min; washing with deionized water, soaking foamed nickel in dilute hydrochloric acid, and ultrasonic cleaning for 10 min; and then washing the mixture by using deionized water, and drying the mixture 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 until completely dissolved, adjusting pH to 6 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing NiSO 40g/L 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) Ultrasonic-assisted electrodeposition for preparing Fe-Ni-Ce catalyst alloy powder
The difference from step (2) in example 1 is that: the temperature of the electrolytic aqueous solution is 40 ℃ during ultrasonic-assisted electrodeposition; the current density is 1.5A/cm 2 The time of ultrasonic-assisted electrodeposition is 10min, and the ultrasonic frequency is 80 kHz. And obtaining the dendritic Fe-Ni-Ce catalyst alloy powder on the cathode after the ultrasonic-assisted electrodeposition is finished. And after the ultrasonic-assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum 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 is determined by ICP-OES inductively coupled plasma spectroscopy 2100DV as follows: 73% of Fe, 18% of Ni and 9% of Ce.
Example 4
(1) Pretreatment of iron nets
Placing the iron net cut into 2cm × 2cm in absolute ethyl alcohol for ultrasonic cleaning for 10 min; washing with deionized water, soaking foamed nickel in dilute hydrochloric acid, and ultrasonic cleaning for 10 min; and then washing the mixture by using deionized water, and drying the mixture 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, and mixingStirring to dissolve completely, adjusting pH to 4 with dilute hydrochloric acid to obtain electrolytic aqueous solution containing 60g/L NiSO 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) Ultrasonic-assisted electrodeposition for preparing Fe-Ni-Ce catalyst alloy powder
The difference from step (2) in example 1 is that: the temperature of the electrolytic aqueous solution is 30 ℃ during ultrasonic-assisted electrodeposition; the current density is 3A/cm 2 The time of ultrasonic-assisted electrodeposition is 5min, and the ultrasonic frequency is 100 kHz. And obtaining the dendritic Fe-Ni-Ce catalyst alloy powder on the cathode after the ultrasonic-assisted electrodeposition is finished. And after the ultrasonic-assisted electrodeposition is finished, carrying out high-speed centrifugation, vacuum 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 is determined by ICP-OES inductively coupled plasma spectroscopy 2100DV as follows: 69% Fe, 25% Ni, 6% Ce.
Example 5
The Fe-Ni-Ce catalyst alloy powder prepared in the embodiments 1-4 of the invention and the FeNi catalyst alloy powder sold in the market are respectively and uniformly mixed with graphite powder according to the proportion of 4:6, and pressed into a cavity synthetic column with the diameter of 39 mm. The diamond synthesis was carried out using a phi 39mm cavity at a pressure of 5.2GPa, a temperature above 1450 ℃, and a heating time of about 20min, and the obtained diamond was subjected to hydrostatic strength, TI, TTI performance tests, the results of which are shown in table 1.
TABLE 1 main performance indexes of Fe-Ni-Ce catalyst alloy powder for synthesizing diamond
As can be seen from table 1, compared with the commercially available FeNi catalyst powder, the Fe-Ni-Ce catalyst alloy powder prepared in the embodiments 1-4 of the present invention can effectively increase the yield per unit of mixture, 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, which indicates that the present invention has good market application prospects.
Claims (10)
1. The Fe-Ni-Ce catalyst alloy powder is characterized in that the Fe-Ni-Ce catalyst alloy powder is prepared by an ultrasonic-assisted electrodeposition process from an electrolyte containing an iron salt, a nickel salt, a cerium salt, a conductive agent and a complexing agent. 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.
2. The Fe-Ni-Ce catalyst alloy powder according to claim 1, wherein the Fe-Ni-Ce catalyst alloy powder comprises the following components in mass percent: 60-79% of Fe, 20-50% of Ni and 1-20% of Ce.
3. A method for preparing the Fe-Ni-Ce catalyst alloy powder according to claim 1, comprising the steps of:
(1) pretreatment of the conductive substrate: cutting the conductive base material into small rectangular pieces, ultrasonically cleaning the cut conductive base material in absolute ethyl alcohol, washing the conductive base material with deionized water, ultrasonically cleaning the conductive base material in dilute hydrochloric acid, cleaning the conductive base material with deionized water, and drying the conductive base material for later use;
(2) preparing an electrolytic aqueous solution: the electrolytic water solution comprises iron 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: and (2) 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 an anode, ultrasonically assisting the electrolytic aqueous solution prepared in the step (2) for electrodeposition, and after the ultrasonic-assisted electrodeposition is finished, carrying out centrifugal separation, vacuum filtration, alcohol washing and vacuum drying on the electrolytic aqueous solution to obtain the Fe-Ni-Ce catalyst alloy powder.
4. The method of claim 3, wherein in step (1), the conductive matrix material is a nickel mesh, Raney nickel, or iron mesh.
5. The method of claim 3, wherein in step (2), the iron salt is one or a mixture of several water-soluble iron salts, the nickel salt is one or a mixture of several water-soluble nickel salts, and the cerium salt is one or a mixture of several water-soluble cerium salts.
6. The method of claim 3, wherein in step (2), the conductive agent comprises an alkali metal inorganic salt and/or a soluble ammonium salt, and the complexing agent is one or a mixture of water-soluble citrate.
7. The method of claim 3, wherein in the step (2), the concentration of the iron salt is 20 to 50g/L, the concentration of the nickel salt is 40 to 60g/L, the concentration of the cerium salt is 1 to 30g/L, the concentration of the conductive agent is 50 to 90g/L, the concentration of the complexing agent is 50 to 100g/L, and the concentration of the boric acid is 20 to 50 g/L.
8. The method of claim 3, wherein the pH of the aqueous electrolytic solution in step (2) is 3 to 7.
9. The method of claim 3, wherein in the step (3), the temperature of the electrolytic aqueous solution during the ultrasonic-assisted electrodeposition is 30 to 80 ℃, and the current density is 0.5 to 3.0A/cm 2 The frequency of the ultrasonic wave is 20-100kHz, and the time of ultrasonic-assisted electrodeposition is 5-20 min.
10. Use of the Fe-Ni-Ce catalyst alloy powder according to claim 1 in the preparation of artificial diamond.
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