CN114570370B - Nickel-based multi-component alloy catalyst and preparation method thereof - Google Patents

Nickel-based multi-component alloy catalyst and preparation method thereof Download PDF

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CN114570370B
CN114570370B CN202210138772.6A CN202210138772A CN114570370B CN 114570370 B CN114570370 B CN 114570370B CN 202210138772 A CN202210138772 A CN 202210138772A CN 114570370 B CN114570370 B CN 114570370B
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alloy catalyst
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CN114570370A (en
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王来军
刘海涛
陈崧哲
张平
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Tsinghua University
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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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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 catalyst is nickel-based multi-component amorphous alloy Ni-M-B composed of metal nickel, metal M and nonmetal boron, wherein the metal M is one or two of cobalt, copper or iron, and the molar ratio of the metal M to the nickel is M: ni is 0.01-1: 0.01 to 1, the molar ratio of metal to nonmetal (Ni+M): b is 1.5-5: 1. the preparation method of the nickel-based multi-component alloy catalyst comprises the main steps of precursor preparation and electroless plating, wherein a boron-containing reducing agent is adopted to reduce salt containing nickel, cobalt, copper or iron, a solid product obtained by reduction is used as a precursor, and the precursor is added into an electroless plating solution, so that the nickel-based multi-component amorphous alloy catalyst is obtained by electroless plating. The catalyst has the advantages of good thermal stability, excellent hydrogenation catalytic performance and the like, and the preparation method has the advantages of easily controlled conditions and simple operation.

Description

Nickel-based multi-component alloy catalyst and preparation method thereof
Technical Field
The application relates to a nickel-based multi-component alloy catalyst and a preparation method thereof, belonging to the field of chemical materials and preparation thereof.
Background
The amorphous alloy has the characteristics of uniform structure, adjustable chemical composition, high unsaturation of surface atomic coordination and the like, so that the amorphous alloy often presents physical and chemical characteristics which are obviously different from those of the crystalline alloy, for example, when the amorphous alloy is used as a catalyst, the amorphous alloy presents excellent catalytic activity and selectivity due to the surface chemical isotropy and more active sites. In particular to a nickel boron (NiB) amorphous alloy catalyst, which has the advantages of low cost, strong anti-toxicity capability, less environmental pollution in the preparation process, difficult spontaneous combustion in the air and the like compared with the traditional skeleton nickel (Raney Ni) catalyst, and has proved to show more excellent catalytic performance in a plurality of catalytic hydrogenation reactions. Therefore, the amorphous alloy material is considered as a novel catalyst with great application prospect for replacing skeleton nickel or noble metal.
However, nickel boron amorphous alloys have poor thermal stability and are relatively susceptible to oxidation, which undoubtedly affects their use as industrial catalysts. The nickel-based boron amorphous alloy catalyst is generally prepared by a traditional chemical reduction method, and the preparation method is generally harsh in preparation conditions, such as low temperature, nitrogen protection and the like, so that the preparation cost is high; and the nickel-based boron amorphous alloy catalyst obtained by the method has unsatisfactory catalytic performance. Therefore, the nickel-boron amorphous alloy is innovatively designed and optimized in terms of composition and preparation method, so that the novel catalyst with excellent catalytic performance and high stability and the preparation method thereof are obtained, and the novel catalyst has important theoretical and practical significance for promoting the development of the amorphous alloy catalyst.
Disclosure of Invention
In view of the above, the present application aims to provide a nickel-based multi-component alloy catalyst, so as to solve the problems of poor stability and non-ideal catalytic performance of the nickel-boron amorphous alloy catalyst. The application also provides a preparation method of the nickel-based multi-component alloy catalyst, which aims to solve the problems of harsh conditions and high preparation cost of the traditional chemical reduction method.
Therefore, in one aspect of the present application, a nickel-based multi-component alloy catalyst is provided, which is a nickel-based multi-component amorphous alloy Ni-M-B composed of metallic nickel, metallic M and non-metallic boron, wherein the metallic M is one or two of cobalt, copper or iron, and the molar ratio of the metallic M to the metallic nickel Ni is 0.01-1: 0.01 to 1, the molar ratio of metal to non-metal B in the catalyst is (Ni+M): b is 1.5-5: 1.
compared with the traditional nickel-boron amorphous alloy NiB catalyst, the nickel-based multi-component alloy catalyst provided by the application has the advantages that one or two of cobalt, copper or iron are introduced as additives, so that the thermal stability and oxidation resistance of the catalyst are improved, and the catalytic activity of the catalyst is also improved.
Another aspect of the present application provides a method for preparing the nickel-based multi-component alloy catalyst, comprising the steps of:
s1, preparing a precursor by a chemical reduction method: preparing a solution containing a precursor metal soluble salt and a reducing agent solution of potassium borohydride or sodium borohydride respectively; adding a reducing agent solution into a solution containing precursor metal soluble salt, stirring for reaction to generate precipitate, stopping reaction when no bubble is generated, centrifuging the precipitate, and washing until a washing solution is neutral to obtain wet precipitate, namely the precursor for preparing the nickel-based multicomponent alloy catalyst;
s2, preparing chemical plating solution: firstly preparing a mixed solution containing metal salt and a complexing agent, then adding a boron-containing reducing agent, and fully and uniformly stirring to obtain a chemical plating solution; wherein the mixed solution contains nickel salt and complexing agent, or compound of M and complexing agent, or compound of nickel salt and M and complexing agent;
the mixed solution of the soluble salt of the precursor metal in step S1 and the solution in step S2 contains at least one nickel salt and at least one soluble salt of cobalt, copper or iron.
S3, electroless plating reaction: and (2) adding the precursor prepared in the step (S1) into the electroless plating solution, stirring and reacting until no bubble is generated, centrifugally separating and washing a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multi-component alloy catalyst.
Compared with the traditional chemical reduction method, the preparation method of the nickel-based multi-component alloy catalyst provided by the application has the advantages that the preparation conditions are mild and easy to control, and the large-scale preparation of the catalyst is easy to realize.
In the above technical scheme, in the step S1, the molar ratio of the nonmetallic boron in the reducing agent solution to the metal in the solution containing the precursor metal soluble salt is 1 to 5:1.
in the above technical solution, the soluble salt of the precursor metal is any one of sulfate, hydrochloride or acetate of nickel, cobalt, copper or iron.
In the above technical scheme, in the step S2, the nickel salt is nickel chloride, nickel sulfate or nickel acetate.
In the above technical scheme, the compound of M is a sulfate, hydrochloride or acetate of cobalt, copper or iron.
In the technical scheme, the complexing agent is any one or a mixture of more of ethylenediamine, ammonia water and tartrate.
In the technical scheme, the boron-containing reducing agent is sodium borohydride, potassium borohydride or dimethylamine borane.
In the above technical scheme, in the step S2, when the mixed solution contains both the nickel salt, the compound of M and the complexing agent, the molar ratio of the metal M to the metal nickel Ni is 0.01-1: 0.01 to 1.
In the above technical solution, in the step S2, the molar ratio of non-metallic boron to metallic Ni and metallic M in the electroless plating solution is B: (Ni+M) is 1 to 5:1.
in the above technical scheme, in the step S3, the pH value of the electroless plating solution is controlled to be 9-14 before the electroless plating reaction, and the temperature of the plating solution is controlled to be 20-90 ℃.
The application has the advantages and beneficial effects that:
(1) Compared with the traditional nickel-boron amorphous alloy NiB catalyst, the nickel-based multi-component alloy catalyst provided by the application has the advantages that one or two of cobalt, copper or iron are introduced as additives, so that the thermal stability and oxidation resistance of the catalyst are improved, and the catalytic activity of the catalyst is also improved.
(2) Compared with the traditional chemical reduction method, the preparation method of the nickel-based multi-component alloy catalyst provided by the application has the advantages that the preparation conditions are mild and easy to control, and the large-scale preparation of the catalyst is easy to realize.
Additional aspects and advantages of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and may be better understood from the following description of embodiments with reference to the accompanying drawings,
wherein:
FIG. 1 is an XRD characterization pattern of Fe-Ni-B produced in example 1 of the present application.
Detailed Description
Embodiments of the present application are described in detail below. The following examples are illustrative and are intended to be illustrative of the application and are not to be construed as limiting the application.
The following describes a nickel-based multi-component alloy catalyst and a preparation method thereof according to an embodiment of the present application.
An embodiment of one aspect of the present application provides a nickel-based multicomponent alloy catalyst, which is a nickel-based multicomponent amorphous alloy Ni-M-B composed of metallic nickel, metallic M and non-metallic boron, wherein the metallic M is one or two of cobalt, copper or iron, and the molar ratio of the metallic M to the metallic nickel Ni is 0.01-1: 0.01 to 1, the molar ratio of metal to non-metal B in the catalyst is (Ni+M): b is 1.5-5: 1.
another embodiment of the present application provides a method for preparing the nickel-based multi-component alloy catalyst, including the following steps:
s1, preparing a precursor by adopting a chemical reduction method: preparing a solution containing a precursor metal soluble salt and a potassium borohydride or sodium borohydride reducing agent solution respectively, and controlling the molar ratio of nonmetal boron to metal to be 1-5: 1.
the boron-containing reducing agent solution is added into the solution containing the precursor metal soluble salt, and the solution is stirred for reaction, so that precipitation is generated, a large amount of bubbles are simultaneously emitted, and the reaction is stopped when no bubbles are generated.
And (3) centrifugally separating and washing the precipitate until the washing liquid is neutral, and obtaining wet precipitate, namely the precursor for preparing the nickel-based multicomponent alloy catalyst.
S2, preparing a nickel-based multicomponent alloy catalyst by adopting an electroless plating method:
preparing chemical plating solution: preparing a mixed solution, adding a boron-containing reducing agent, and fully and uniformly stirring to obtain the chemical plating solution. Wherein the mixed solution contains nickel salt and complexing agent, or compound of M and complexing agent, or nickel salt, compound of M and complexing agent.
The mixed solution of the precursor metal soluble salt in step S1 and step S2 contains nickel salt in at least one place and cobalt, copper or iron soluble salt in at least one place. That is, if the mixed solution contains a nickel salt and a complexing agent, the soluble salt of the precursor metal contains at least any one of the sulfate, hydrochloride, or acetate salts of cobalt, copper, or iron (i.e., metal M). If the mixed solution contains a compound of M and a complexing agent, the soluble salt of the precursor metal contains at least one of a sulfate, a hydrochloride, or an acetate of nickel. If the mixed solution contains nickel salt, M compound and complexing agent, the precursor metal soluble salt contains any one of sulfate, hydrochloride or acetate of nickel, cobalt, copper or iron.
The molar ratio of nonmetal to metal in the electroless plating solution is B: (Ni+M) is 1 to 5:1, a step of; when the mixed solution contains nickel salt, a compound of M and a complexing agent, the molar ratio of metal M to metal nickel Ni is 0.01-1: 0.01 to 1.
S3, electroless plating reaction: controlling the pH value of the chemical plating solution to be 9-14, and controlling the temperature of the plating solution to be 20-90 ℃. And (3) adding the wet precipitate obtained in the step (S1) into the electroless plating solution, stirring and reacting until no bubble is generated, and carrying out centrifugal separation and washing on a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multicomponent alloy catalyst.
In some embodiments, the precursor metal-soluble salt is any one of a sulfate, hydrochloride, or acetate of nickel, cobalt, copper, or iron.
In some embodiments, in step S2, the nickel salt is nickel chloride, nickel sulfate, or nickel acetate.
In some embodiments, the compound of M is a sulfate, hydrochloride, or acetate salt of cobalt, copper, or iron.
In some embodiments, the complexing agent is a mixture of any one or more of ethylenediamine, ammonia, and tartrate.
In some embodiments, the boron-containing reducing agent is sodium borohydride, potassium borohydride, or dimethylamine borane.
In the preparation process, the composition of the finally prepared nickel-based multicomponent alloy catalyst can be regulated and controlled by controlling the dosage of the precursor, the concentration of different components (especially nickel, M and reducing agent) of the electroless plating solution, the volume dosage of the electroless plating solution and the time of the electroless plating reaction.
The present application will be described in detail by way of examples.
Example 1: preparation of 0.15Fe-Ni-B (the values given above for Fe represent the control of the material to Ni molar ratio of 0.15)
Firstly, preparing a precursor FeB by adopting a chemical reduction method: preparing a solution containing ferrous chloride and a solution of a potassium borohydride reducing agent respectively; weigh 0.895g FeCl 2 ·4H 2 O (equivalent to 0.0045 mol) was added to the beaker and was dissolved thoroughly by adding 50ml of deionized water, and 0.4851g of potassium borohydride KBH was weighed again 4 (reduced to 0.009 mol) into another beaker, and added with 10ml deionized water to dissolve thoroughly, the molar ratio of non-metallic boron to metallic iron was 2:1, a step of; adding a potassium borohydride reducer solution into a ferrous chloride solution, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet precipitation, namely preparing the precursor iron boride of the nickel-based multicomponent alloy Fe-Ni-B catalyst.
Then adopting an electroless plating method to prepare a nickel-based multicomponent alloy Fe-Ni-B catalyst: i) Preparing chemical plating solution: firstly preparing a mixed solution containing nickel salt nickel chloride (0.1M), complexing agent potassium sodium tartrate (0.06M) and ethylenediamine (1.0M), then adding a reducing agent potassium borohydride, and fully and uniformly stirring to obtain a chemical plating solution, wherein the molar ratio of nonmetal boron to metal nickel is B: ni is 2.5:1. ii) electroless plating reaction: adding a proper amount of sodium hydroxide to control the pH value of the chemical plating solution to be 14, controlling the temperature of the plating solution to be 80 ℃, adding the obtained wet precipitation precursor ferric boride into the 300mL of chemical plating solution, stirring and reacting until no bubble is generated, centrifugally separating and washing a solid product until the washing solution is neutral, wherein the obtained solid is a nickel-based multicomponent alloy Fe-Ni-B catalyst, and preparing the material consumption ratio of Fe: ni molar ratio of 0.15:1, XRD characterization is carried out on the Fe-Ni-B, the result is shown in figure 1, the spectrum shows a dispersion-width peak between 40 and 50 degrees 2 theta, which is the characteristic diffraction peak of the nickel-based amorphous alloy, no sharp crystal diffraction peak is found in the spectrum, the catalyst is in an amorphous structure, and the atomic composition of the catalyst is Fe by ICP measurement 10.5 Ni 68.1 B 21.4 。
Example 2: preparation of 0.01Fe-Ni-B
The preparation is the same as in example 1, except that the FeB is used in an amount of1/15 of example 1, the other electroless nickel plating solutions were used in the same amounts to control Fe: the molar ratio of Ni is 0.01; the atomic composition of the catalyst is Fe by ICP measurement 0.8 Ni 79.2 B 20 。
Example 3: preparation of 0.05Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 1/3 of that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.05. The atomic composition of the catalyst is Fe by ICP measurement 3.5 Ni 76.5 B 20 。
Example 4: preparation of 0.1Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 2/3 of that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.1. The atomic composition of the catalyst is Fe by ICP measurement 7 Ni 73 B 20 。
Example 5: preparation of 0.2Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 4/3 of that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.2.
Example 6: preparation of 0.3Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 2 times that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.3.
Example 7: preparation of 0.4Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 8/3 times that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.4.
Example 8: preparation of 0.5Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 10/3 times that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 0.5.
Example 9: preparation of 1Fe-Ni-B
The preparation process is the same as in example 1 except that the amount of FeB is 20/3 times that of example 1, and the other processes such as electroless nickel plating solution are the same, so that Fe is controlled: the molar ratio of Ni was 1.
Example 10: preparation of 1Fe-0.1Ni-B
The preparation process was the same as in example 9 except that the electroless nickel plating solution was used in an amount 1/10 times that of example 9, i.e., the plating solution had the same composition as in example 1, and the plating solution had a volume of 30mL, thereby controlling Fe: the molar ratio of Ni was 1:0.1.
Example 11: preparation of 1Fe-0.01Ni-B
The procedure is as in example 10, except that the concentrations of the components in the electroless nickel plating solution are 1/100 times that of example 9, thereby controlling Fe: the molar ratio of Ni is 1:0.01.
Example 12: preparation of 0.15Fe-0.05Cu-1Ni-B
The preparation process is the same as in example 1, except that the electroless plating solution also contains 0.005M copper chloride, so that the molar ratio of Fe to Cu to Ni is controlled to be 0.15:0.05:1.
Example 13: preparation of 0.15Fe-0.05Co-1Ni-B
The preparation process is the same as in example 1, except that the electroless plating solution also contains 0.005M cobalt chloride, so that the molar ratio of Fe to Co to Ni is controlled to be 0.15:0.05:1.
Example 14: preparation of 0.15Fe-1Co-0.01Ni-B
The preparation process was the same as in example 13 except that the electroless plating solution had a nickel chloride concentration of 0.001M and a cobalt chloride concentration of 0.1M, thereby controlling the molar ratio of Fe to Co to Ni to be 0.15:1:0.01.
Example 15:0.15 preparation of Co-Ni-B (the numerical values before Co represent the control of the material to Co: ni molar ratio at the time of preparation to be 0.15)
The preparation process is the same as in example 1, except that ferrous chloride is changed into cobalt chloride, and the specific process is as follows: first, a chemical reduction method is adopted to prepare a precursor CoB: preparing a solution containing a precursor metal soluble salt cobalt chloride and a solution of a potassium borohydride reducing agent respectively; weigh 0.584g CoCl 2 (equivalent to 0.0045 mol) into a beaker, and 50ml of deionized water was added for complete dissolution, and 0.4851g of potassium borohydride KBH was weighed 4 (folding)0.009 mol) was added to another beaker and 10ml deionized water was added to dissolve thoroughly, the molar ratio of non-metallic boron to metallic iron being 2:1, a step of; adding a potassium borohydride reducer solution into a ferrous chloride solution, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet precipitate, namely preparing the precursor CoB of the nickel-based multicomponent alloy Co-Ni-B catalyst.
Then adopting an electroless plating method to prepare a nickel-based multicomponent alloy Co-Ni-B catalyst: i) Preparing chemical plating solution: firstly preparing a mixed solution containing nickel salt nickel chloride (0.1M), complexing agent potassium sodium tartrate (0.6M) and ethylenediamine (1.0M), then adding a reducing agent potassium borohydride, and fully and uniformly stirring to obtain a chemical plating solution, wherein the molar ratio of nonmetal to metal is B: ni is 2.5:1. ii) electroless plating reaction: adding a proper amount of sodium hydroxide to control the pH value of the chemical plating solution to be 14, controlling the temperature of the plating solution to be 80 ℃, adding the obtained wet precipitate into the 300mL of chemical plating solution, stirring and reacting until no bubble is generated, centrifuging and washing a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multicomponent alloy 0.15Co-Ni-B catalyst.
Example 16: preparation of 0.15Co-0.01Cu-1Ni-B
Preparation of nickel-based multicomponent alloy Co-Cu-Ni-B catalyst precursor CoB the procedure of example 15 was followed except that sodium borohydride was used as the reducing agent, the molar ratio of non-metallic boron to metallic cobalt was 1:1, a step of; preparing a mixed solution containing nickel salt nickel chloride (0.1M), copper chloride (0.001M) and ethylenediamine (1.0M), adding a reducing agent potassium borohydride, and fully and uniformly stirring to obtain a chemical plating solution, wherein the molar ratio of nonmetal to metal is B: ni is 1:1, a step of; adding a proper amount of sodium hydroxide into the chemical plating solution to control the pH value of the chemical plating solution to be 12, wherein the temperature of the plating solution is 55 ℃, adding the obtained CoB precursor into the 300mL of chemical plating solution, stirring and reacting until no bubble is generated, centrifugally separating and washing a solid product until the washing solution is neutral, and obtaining the solid which is the nickel-based multicomponent alloy 0.15Co-0.01Cu-1Ni-B catalyst.
Example 17: preparation of 1Ni-1Co-B
FirstThe precursor NiB is prepared by adopting a chemical reduction method: preparing a solution containing precursor metal soluble salt nickel sulfate and a solution of potassium borohydride reducing agent respectively; 1.314g (0.005 mol in terms of) of nickel sulfate hexahydrate was weighed into a beaker, 50ml of deionized water was added for sufficient dissolution, and 0.2695g (0.005 mol in terms of) of potassium borohydride (KBH) 4 ) Another beaker was added and 50ml of deionized water was added to dissolve thoroughly, with a controlled molar ratio of nonmetallic boron to metallic nickel of 1:1, a step of; adding a potassium borohydride reducer solution into a nickel sulfate solution, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet precipitation, namely preparing nickel boride, namely NiB, which is a precursor of the nickel-based multicomponent alloy Ni-Co-B catalyst.
Then adopting an electroless plating method to prepare a nickel-based multicomponent alloy Ni-Co-B catalyst: i) Preparing chemical plating solution: firstly preparing a mixed solution containing nickel salt cobalt chloride (0.05M) and ethylenediamine (0.4M), then adding a reducing agent potassium borohydride, and fully and uniformly stirring to obtain a chemical plating solution, wherein the molar ratio of nonmetal to metal, namely, the molar ratio of B is 1:1. ii) electroless plating reaction: adding a proper amount of ammonia water to control the pH value of the chemical plating solution to be 9, adding wet precursor NiB into the 100mL of chemical plating solution at the temperature of 20 ℃, stirring and reacting until no bubble is generated, centrifugally separating and washing a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multicomponent alloy 1Ni-1Co-B catalyst, and the material consumption ratio Ni:Co molar ratio is 1:1. the atomic composition of the catalyst was about Ni as measured by ICP 41.5 Cu 41.9 B 16.6 。
Example 18: preparation of 0.5Ni-1Co-B
The procedure is as in example 17, but the nickel salt used in the preparation of the precursor NiB is nickel acetate and the molar ratio of non-metallic boron to metallic nickel is controlled to be 5:1, the electroless plating solution is different from example 16 in that the reducing agent in the electroless plating solution adopts dimethylamine borane, and the molar ratio of nonmetal to metal, namely B, ni is 5:1, controlling the pH value of the chemical plating solution to be 14, controlling the temperature of the plating solution to be 90 ℃, controlling the dosage of the plating solution to be 200mL, and obtaining solid which is nickel-based multicomponent alloy 0.5Ni-1Co-B, catalyzingAtomic composition of about Ni 20.9 Cu 40.1 B 39 。
Example 19:0.15 preparation of Cu-Ni-B (the numerical values before Cu represent the control of the material amount to Cu: ni molar ratio at the time of preparation was 0.15)
The preparation process is the same as in example 1, except that ferrous chloride is changed into copper chloride, and the specific process is as follows: preparing a solution containing precursor metal soluble salt copper chloride and a solution of potassium borohydride reducing agent respectively; weigh 0.767g CuCl 2 ·2H 2 O (equivalent to 0.0045 mol) was added to the beaker and was dissolved thoroughly by adding 50ml of deionized water, and 0.4851g of potassium borohydride KBH was weighed again 4 (reduced to 0.009 mol) into another beaker, and added with 10ml deionized water to dissolve thoroughly, the molar ratio of non-metallic boron to metallic iron was 2:1, a step of; adding a potassium borohydride reducer solution into a ferrous chloride solution, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet precipitation, namely the precursor for preparing the nickel-based multi-component alloy Cu-Ni-B catalyst.
Then adopting an electroless plating method to prepare a nickel-based multicomponent alloy Cu-Ni-B catalyst: i) Preparing chemical plating solution: firstly preparing a mixed solution containing nickel salt nickel chloride (0.1M), complexing agent potassium sodium tartrate (0.6M) and ethylenediamine (1.0M), then adding a reducing agent potassium borohydride, and fully and uniformly stirring to obtain a chemical plating solution, wherein the molar ratio of nonmetal to metal is B: ni is 2.5:1. ii) electroless plating reaction: adding a proper amount of sodium hydroxide to control the pH value of the chemical plating solution to be 14, the temperature of the plating solution to be 80 ℃, adding the obtained wet precipitate into the 300mL of chemical plating solution, stirring and reacting until no bubble is generated, centrifuging and washing a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multicomponent alloy 0.15Cu-Ni-B catalyst.
Example 20: preparation of 0.15Cu-0.2Ni-B
The wet precipitated precursor was prepared in the same manner as in example 19, and an electroless plating solution containing nickel sulfate (0.1M), ethylenediamine, potassium borohydride and sodium hydroxide was prepared, wherein the molar ratio of non-metallic boron to metallic iron in the plating solution was 2:1, the pH value of the plating solution is 14, the temperature of the plating solution is 45 ℃, the obtained wet precipitate is added into the 300mL of chemical plating solution, the stirring reaction is carried out for 10min, the centrifugal separation and washing are carried out on the solid product until the washing solution is neutral, and the obtained solid is the nickel-based multicomponent alloy 0.15Cu-0.2Ni-B catalyst.
Comparative example 1: preparation of hx-0.15Fe-Ni-B by conventional chemical reduction (hx stands for chemical reduction)
Firstly, preparing mixed solutions of soluble salts containing nickel and iron respectively, and weighing 0.895g FeCl respectively 2 ·4H 2 O (equivalent to 0.0045 mol) and 3.888g NiCl 2 (reduced by 0.03 mol) into a beaker, and 380ml of deionized water was added for complete dissolution, and 3.4722g of potassium borohydride KBH was weighed 4 (0.069 mol) adding another beaker, adding 80ml of deionized water for full dissolution, adding the potassium borohydride reducing agent solution into the mixed solution of ferrous chloride and nickel chloride, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet solid precipitate which is hx-0.15Fe-Ni-B obtained by a conventional reduction method.
Comparative example 2: preparation of hx-0.15Co-Ni-B by conventional chemical reduction method
Firstly, a mixed solution of soluble salts containing nickel and cobalt respectively is prepared, and 0.584g of CoCl is weighed respectively 2 (equivalent to 0.0045 mol) and 3.888g NiCl 2 (reduced by 0.03 mol) into a beaker, and 380ml of deionized water was added for complete dissolution, and 3.4722g of potassium borohydride KBH was weighed 4 (0.069 mol) adding another beaker, adding 80ml of deionized water for full dissolution, adding the potassium borohydride reducing agent solution into the mixed solution of ferrous chloride and nickel chloride, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet solid precipitate which is hx-0.15Co-Ni-B obtained by a conventional reduction method.
Comparative example 3: preparation of hx-0.15Cu-Ni-B by conventional chemical reduction method
Firstly, a mixed solution of soluble salts containing nickel and copper is prepared, and 0.767g of the mixed solution is weighedCuCl 2 ·2H 2 O (equivalent to 0.0045 mol) and 3.888g NiCl 2 (reduced by 0.03 mol) into a beaker, and 380ml of deionized water was added for complete dissolution, and 3.4722g of potassium borohydride KBH was weighed 4 (0.069 mol) adding another beaker, adding 80ml of deionized water for full dissolution, adding the potassium borohydride reducing agent solution into the mixed solution of ferrous chloride and nickel chloride, stirring for reaction to generate precipitation, simultaneously emitting a large amount of bubbles, and stopping the reaction when no bubbles are generated; and (3) centrifugally separating and washing the reaction product until the washing liquid is neutral, and obtaining wet solid precipitate which is hx-0.15Cu-Ni-B obtained by a conventional reduction method.
Catalytic performance experiments of the samples:
the activity of the catalyst was evaluated using sulfolane catalyst hydrogenation as a probe reaction: the reaction was carried out in a WZDC-100 data acquisition autoclave manufactured by WZDC technology Co., ltd., beijing, at 65℃and at 600r/min stirring speed, at 3.2MPa, 2.0g of catalyst in wet form (5 min for centrifugation at 3000 r/min), 5.0g of sulfolane (analytically pure, shanghai Michelin Biochemical Co., ltd.) in the form of a solution, 50mL of deionized water, and 4 hours. The product concentration was analyzed by gas chromatography to calculate the conversion of sulfolane.
TABLE 1 comparison of results of catalyst Activity (sulfolane conversion)
Comparison of experimental results (shown in Table 1) of catalyst activity (sulfolane conversion) can show that the hx-0.15Fe-Ni-B, hx-0.15Co-Ni-B, hx-0.15Cu-Ni-B catalytic sulfolane hydrogenation conversion rate prepared by the traditional chemical reduction method (comparative examples 1, 2 and 3) is lower, namely 20.7%, 16.0% and 18.0% respectively; under the same reaction conditions, the traditional Raney Ni catalyst has about 32 percent of the hydrogenated conversion rate of the sulfolane, the NiB catalyst prepared by adopting a chemical reduction method has about 33.7 percent of the hydrogenated conversion rate of the sulfolane, and the 0.15Fe-Ni-B, 0.15Co-Ni-B and 0.15Cu-Ni-B prepared by adopting the method (such as examples 1, 15 and 19) have lower hydrogenated conversion rates of the sulfolane which are similar in composition and are 79.7 percent, 34.0 percent and 37.0 percent respectively; these results demonstrate that the activity (sulfolane conversion) of the nickel-based multi-alloy catalyst prepared by the process of the present application is not only higher than Raney Ni and NiB catalysts, but also much higher than nickel-based alloy catalysts prepared by conventional chemical reduction processes. One of the main reasons for analyzing the activity difference is that the nickel-based boron alloy catalyst prepared by the traditional chemical reduction method has poor stability, the surface is easily oxidized by oxygen in the air, and the nickel-based boron alloy catalyst prepared by the method of firstly reducing and then chemically plating has better stability; in addition, the preparation method of the nickel-based multi-component alloy catalyst provided by the application has mild and easily controlled preparation conditions, and is easy to realize the large-scale preparation of the catalyst.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.

Claims (10)

1. The preparation method of the nickel-based multi-component alloy catalyst is characterized by comprising the following steps:
s1, preparing a precursor by a chemical reduction method: preparing a solution containing a precursor metal soluble salt and a reducing agent solution of potassium borohydride or sodium borohydride respectively; adding a reducing agent solution into a solution containing precursor metal soluble salt, stirring for reaction to generate precipitate, stopping reaction when no bubble is generated, centrifuging the precipitate, and washing until a washing solution is neutral to obtain wet precipitate, namely the precursor for preparing the nickel-based multicomponent alloy catalyst; wherein the precursor metal soluble salt is any one of sulfate, hydrochloride or acetate of nickel, cobalt, copper or iron;
s2, preparing chemical plating solution: firstly preparing a mixed solution containing metal salt and a complexing agent, then adding a boron-containing reducing agent, and fully and uniformly stirring to obtain a chemical plating solution; wherein the mixed solution contains nickel salt and a complexing agent, or a compound of M and the complexing agent, or the nickel salt, the compound of M and the complexing agent, and M is one or two of cobalt, copper or iron;
at least one part of the mixed solution of the precursor metal soluble salt in the step S1 and the mixed solution in the step S2 contains nickel salt, and at least one part contains soluble salt of cobalt, copper or iron;
s3, electroless plating reaction: and (2) adding the precursor prepared in the step (S1) into the electroless plating solution, stirring and reacting until no bubble is generated, centrifugally separating and washing a solid product until the washing solution is neutral, wherein the obtained solid is the nickel-based multi-component alloy catalyst.
2. The method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein in the step S1, the molar ratio of non-metallic boron in the reducing agent solution to metal in the solution containing the precursor metal soluble salt is 1 to 5:1.
3. the method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein in the step S2, the nickel salt is nickel chloride, nickel sulfate or nickel acetate.
4. The method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein the compound of M is a sulfate, hydrochloride or acetate of cobalt, copper or iron.
5. The method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein the complexing agent is a mixture of any one or more of ethylenediamine, ammonia water and tartrate.
6. The method of preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein the boron-containing reducing agent is sodium borohydride, potassium borohydride or dimethylamine borane.
7. The method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein in the step S2, the molar ratio of non-metallic boron to metallic Ni and metallic M in the electroless plating solution is B: (Ni+M) is 1 to 5:1.
8. the method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein in the step S2, when the mixed solution contains a nickel salt, a compound of M and a complexing agent, the molar ratio of metal M to metal nickel Ni is 0.01-1: 0.01 to 1.
9. The method for preparing a nickel-based multi-component alloy catalyst according to claim 1, wherein in the step S3, the pH of the electroless plating solution is controlled to be 9-14 and the temperature of the electroless plating solution is controlled to be 20-90 ℃.
10. The nickel-based multi-component alloy catalyst prepared by the preparation method of any one of claims 1-9, which is characterized in that the nickel-based multi-component amorphous alloy Ni-M-B is composed of metallic nickel, metallic M and non-metallic boron, wherein the molar ratio of the metallic M to the metallic nickel Ni is 0.01-1: 0.01 to 1, and the molar ratio of metal to nonmetal B in the catalyst, namely (Ni+M), B is 1.5 to 5:1.
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CN101024181A (en) * 2007-03-09 2007-08-29 南开大学 Non-crystal-state alloy catalyst for preparing maltol by malt sugar hydrogenation, and its preparing method
WO2016155313A1 (en) * 2015-03-31 2016-10-06 南通瑞翔新材料有限公司 High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor
CN112221502A (en) * 2020-09-29 2021-01-15 清华大学 Hollow spherical shell carrier loaded nickel-based alloy catalyst and preparation method thereof

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FR1580252A (en) * 1967-06-05 1969-09-05
CN1792440A (en) * 2006-01-12 2006-06-28 南开大学 Method for preparing NiB non-crystalline alloy catalyst with the aid of microwave
CN101007281A (en) * 2007-01-26 2007-08-01 南开大学 Novel preparation method of amorphous alloy catalyst
CN101024181A (en) * 2007-03-09 2007-08-29 南开大学 Non-crystal-state alloy catalyst for preparing maltol by malt sugar hydrogenation, and its preparing method
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