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CN118059871B - Ni-M1-M2-M3 medium entropy intermetallic compound catalyst and preparation method and application thereof - Google Patents

Ni-M1-M2-M3 medium entropy intermetallic compound catalyst and preparation method and application thereof Download PDF

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CN118059871B
CN118059871B CN202410471696.XA CN202410471696A CN118059871B CN 118059871 B CN118059871 B CN 118059871B CN 202410471696 A CN202410471696 A CN 202410471696A CN 118059871 B CN118059871 B CN 118059871B
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catalyst
intermetallic compound
preparing
compound catalyst
nitrate
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CN118059871A (en
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葛小虎
井运道
曹约强
梁逸晶
段学志
钱刚
张晶
周兴贵
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East China University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/825Catalysts 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 gallium, indium or thallium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/80Catalysts 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 zinc, cadmium or mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/83Catalysts 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a Ni-M1-M2-M3 medium entropy intermetallic compound catalyst, a preparation method and application thereof, wherein active metal components M1 and M2 In the medium entropy intermetallic compound catalyst are selected from one of Fe, co and Cu, M1 and M2 are different, and an inert metal component M3 is selected from one of Ga, in and Zn; four metals in the catalyst jointly form Ni-M1-M2-M3 multi-tooth diamond active sites, and a Ni-M1-M2-M3 quadruple site structure rich in electrons Ni, M1 and M2 and deficient in electrons M3 is formed. The catalyst has the advantages of high alkyne hydrogenation catalytic activity, good selectivity and good stability, realizes high-efficiency catalytic reaction at low temperature, and avoids aggravation of green oil generation at high temperature.

Description

Ni-M1-M2-M3 medium entropy intermetallic compound catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an entropy intermetallic compound catalyst in Ni-M1-M2-M3, and a preparation method and application thereof.
Background
In the ethylene industry, the selective hydrogenation of acetylene and propyne is one of the main processes in ethylene refining processes. The crude ethylene steam produced by the naphtha steam cracking system contains 0.5-2% of acetylene by volume fraction, and in order to obtain polymerization grade ethylene, the crude ethylene steam needs to be subjected to selective hydrogenation to reduce the acetylene content to below 5 ppm and reduce the propyne content to 5-10 ppm. In theory, the ethylene is purified by a plurality of methods such as a solvent absorption method, an acetylene copper precipitation method, a low-temperature rectification extraction method, catalytic hydrogenation and the like, but the acetylene selective hydrogenation technology is widely used in industry based on the cost and efficiency considerations of the prior art. The process can not only remove trace acetylene in ethylene products, but also increase the yield of ethylene. However, acetylene and propyne are susceptible to deep hydrogenation in hydrogenation processes to produce ethane and propane, respectively, and are also susceptible to catalyst deactivation by oligomerization to produce "green oil".
Highly optimized PdAg catalysts are currently commonly used in industry to reduce the activity of deep hydrogenation of acetylene to increase catalyst selectivity. However, the microstructure of the PdAg catalyst has disorder, the surface of the catalyst still has a multidentate adsorption configuration, and the weakening effect on the activity of deep acetylene hydrogenation is not obvious. In order to optimally upgrade the existing industrial catalyst and design a novel efficient, stable and low-cost catalyst, researchers have recently focused on the characteristic of non-noble metal Ni for selective hydrogenation of alkyne, for example, journal literature 2008, 320:1320-1322 reports modification of Ni active sites by a second metal component, and the geometric structure and electronic properties of the Ni catalyst are regulated, so that the selectivity of alkene is improved. However, the binary Ni-based metal compound catalyst has limited composition diversity, so the electronic properties and the geometric configuration are limited in regulation range, and the catalyst cannot reach the optimal surface for alkyne hydrogenation. Based on the prior art, the cost of noble metal Pd adopted in alkyne hydrogenation catalyst is too high, and the performance upper limit of the existing binary Ni-based catalyst is not high, so that a novel Ni-based alloy intermetallic compound multifunctional active site catalyst needs to be developed for selective hydrogenation of acetylene or propyne.
Disclosure of Invention
In view of the above, the invention provides a catalyst of an entropy intermetallic compound in Ni-M1-M2-M3 and a preparation method thereof, which form a multidentate diamond active site which is favorable for acetylene adsorption and a Ni active site which is favorable for ethylene desorption, thereby improving the selectivity of olefin and effectively solving the limitation of low hydrogenation performance of a non-noble metal catalyst.
In order to achieve the above purpose, the technical scheme of the invention is as follows: an entropy intermetallic compound catalyst In Ni-M1-M2-M3, wherein the active metal components M1 and M2 are selected from one of Fe, co and Cu, M1 and M2 are different, and the inert metal component M3 is selected from one of Ga, in and Zn; four metals in the catalyst jointly form Ni-M1-M2-M3 multi-tooth diamond active sites, and a Ni-M1-M2-M3 quadruple site structure rich in electrons Ni, M1 and M2 and deficient in electrons M3 is formed.
The molar ratio of the entropy intermetallic compound catalyst in the Ni-M1-M2-M3, namely the metal Ni, M1, M2 and M3 is 1:1:1:1.
The entropy intermetallic compound catalyst in the Ni-M1-M2-M3 provided by the invention has the advantages that four metals Ni, M1, M2 and M3 in the catalyst jointly form a surface active site with a unique structure, the geometric structure and the electronic position of the active site are regulated and controlled jointly, and a Ni-M1-M2-M3 multidentate diamond active site which is favorable for alkyne adsorption and a Ni active site which is favorable for olefin desorption are formed; the local electron cloud structure of the active metals Ni, M1 and M2 is regulated and controlled by the low electronegativity inert metal M3, so that a Ni-M1-M2-M3 quadruple site structure rich in electrons Ni, M1 and M2 and lacking electrons M3 in isolation is formed.
The invention also provides a preparation method of the entropy intermetallic compound catalyst in Ni-M1-M2-M3, which comprises the following steps:
(1) Preparing nitrate of Ni, M1, M2, M3, mg and Al into mixed metal nitrate solution, and preparing a Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M by adopting a coprecipitation method;
(2) Carrying out vacuum suction filtration, washing and drying on the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M obtained in the step (1), and then carrying out thermal reduction treatment to obtain an entropy intermetallic compound catalyst;
Wherein M1 and M2 are selected from one of Fe, co and Cu, M1 and M2 are different, and M3 is selected from one of Ga, in and Zn; in the step (1), the molar ratio of Ni, M1, M2, M3, mg and Al ions in the mixed metal nitrate solution is 1 (0.95-1.05): (14-17): (4-6).
Based on the composition and element adjustable characteristics of a main plate layer of the layered double hydroxide material, the preparation method utilizes a coprecipitation method to prepare the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material, and then the Ni-M1-M2-M3 medium entropy intermetallic compound catalyst is obtained through reduction.
Preferably, in the step (1), the molar ratio of Ni, M1, M2, M3, mg and Al ions in the mixed metal nitrate solution is 1:1:1:1, (14-17) and (4-6).
The invention further provides that in the step (1), the ion concentration of Ni in the mixed metal nitrate solution is 0.03-0.05 mol/L.
The invention is further configured such that in step (1), the nitrate salt of Ni, fe, co, cu, ga, in, zn, mg, al is nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, copper nitrate trihydrate, gallium nitrate nonahydrate, indium nitrate nonahydrate, zinc nitrate hexahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, respectively.
The invention is further provided that in the step (1), mixed metal nitrate solution and pH regulator are added into the precipitant at the same time under the condition of stirring, the temperature of the reaction system is maintained at 60-70 ℃, and the pH value of the reaction system is controlled at 10+/-1; and after the material feeding is finished, continuing stirring and reacting for 14-18 h, and finally filtering, washing and drying to obtain the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M.
The invention is further arranged to control the adding rate of the mixed metal nitrate solution to be 0.9+/-0.2 mL/min; preferably 1.0 mL/min.
The invention further provides that in the step (1), the pH value of the reaction system is controlled to be 10.
The invention further provides that in the step (1), the drying condition is 80+/-5 ℃ and the drying time is 6-18 hours.
The invention is further arranged that the precipitant is selected from one of sodium carbonate solution, ammonia water, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution.
The invention is further arranged that the pH regulator is selected from one of sodium bicarbonate solution, potassium hydroxide solution and sodium hydroxide solution.
Preferably, the pH regulator is sodium hydroxide solution, and the molar concentration of the sodium hydroxide solution is 2.5+/-0.2 mol/L.
The invention further provides that in the step (2), the thermal reduction temperature is 600-1000 ℃, the reduction time is 2-6H, and the reducing gas is H 2/N2 mixed atmosphere.
The temperature of the thermal reduction is reasonably selected within the range of 600-1000 ℃ according to different peak positions of H 2 -TPR, and the reduction time is properly adjusted within 2-6 hours according to the selection of the reduction temperature. The reduction reaction time may be appropriately prolonged on the basis of this.
Preferably, the reduction temperature is 900 ℃ and the reduction time is 4h.
When the thermal reduction temperature is lower than 600 ℃, the reduction reaction speed is slower, the medium entropy alloy Ni-M1-M2-M3 metal particles grow slower, the granularity is minimum, the smaller Ni-M1-M2-M3 particles easily penetrate into the pore canal of the Mg-Al oxide carrier, the dispersity measured by chemical adsorption is reduced, the number of active sites on the surface of the catalyst is reduced, and the catalyst effect is poor. When the thermal reduction temperature is higher than 1000 ℃, the reduction reaction rate is faster, the Ni-M1-M2-M3 particles grow faster, the granularity is larger, the dispersity measured by chemical adsorption is reduced, the number of active sites on the surface of the catalyst is reduced, and the catalytic effect is poor. When the reduction temperature is 900 ℃, the reduction reaction speed is moderate, the obtained Ni-M1-M2-M3 particles are uniformly loaded on the surface of the carrier, the dispersity measured by chemical adsorption is highest, the number of active sites on the surface of the catalyst is the largest, and the catalytic effect is good.
The invention also provides application of the catalyst of the entropy intermetallic compound in Ni-M1-M2-M3, which is used for the reaction of preparing ethylene by selective hydrogenation of acetylene or preparing propylene by selective hydrogenation of propyne.
The invention is further configured that the hydrogenation reaction conditions are as follows: the temperature is 20-130 ℃ and the pressure is normal; preferably 100-130 ℃; further preferably 110 to 130 ℃.
The invention further provides that in the catalytic hydrogenation reaction for preparing ethylene by selective hydrogenation of acetylene, the gas composition is as follows: 0.5-1.0% of acetylene, 40-60% of ethylene, 5-15% of hydrogen and the balance of nitrogen.
The invention further provides that in the catalytic hydrogenation reaction for preparing propylene by selectively hydrogenating propyne, the gas composition is as follows: 0.5-1.0% of propyne, 10-15% of propylene, 5-10% of hydrogen and the balance of nitrogen.
In the catalytic reaction, it is common to remove a trace amount of alkyne impurities in ethylene or propylene gas in industrial applications.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the Ni-M1-M2-M3 medium entropy intermetallic compound catalyst, provided by the invention, the main body laminate composition and the element adjustable characteristics of the layered double hydroxide material are utilized to prepare the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide, and the subsequent thermal reduction process is combined to realize the controllable preparation of different Ni-M1-M2-M3 medium entropy intermetallic compound catalysts. And combined with thermal reduction treatment, the medium-entropy alloy metal particles Ni-M1-M2-M3 and Mg-Al-O metal oxide are generated simultaneously, so that a stronger effect exists between the generated alloy particles and the metal oxide, and the phenomenon of metal particle agglomeration caused by high-temperature roasting and high-temperature thermal reduction in the traditional impregnation method is avoided, thereby improving the utilization rate of active components Ni and M1 and M2 and improving the catalytic activity.
(2) The synergistic effect of the quadruple sites Ni-M1-M2-M3 in the catalyst strengthens the adsorption of the multidentate diamond sites on acetylene, and is beneficial to the subsequent selective hydrogenation of acetylene; thanks to the regulation and control of the inert sites M3 around the Ni sites on the electronic properties, the adsorption energy of ethylene is reduced, so that the desorption of ethylene is enhanced, and the generation of ethane or green oil by excessive hydrogenation of ethylene is avoided.
(3) Compared with the traditional binary Ni-based catalyst, the catalyst of the entropy intermetallic compound in the Ni-M1-M2-M3 has the characteristics of good catalyst activity, good selectivity and long service life due to the introduction of various active and inert components, so that acetylene and propyne can be completely converted in a set temperature range, and the generation of green oil is prevented from being aggravated at high temperature. Meanwhile, the non-noble metal is adopted as a synthetic material, so that the cost of the existing catalyst for preparing ethylene by acetylene hydrogenation and propylene by propyne hydrogenation is greatly reduced, and the catalyst has good industrial application prospect.
Drawings
FIG. 1 is a schematic diagram of the structures of the catalyst numbers X5-900-4, X8-900-4 and X11-900-4 of the invention.
FIG. 2 is an XRD spectrum of Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the example of the present invention.
FIG. 3 is a transmission electron microscopic image of Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the example of the present invention.
FIG. 4 is a photograph of a transmission electron microscope elemental analysis of Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the example of the present invention.
FIG. 5 a is a transmission electron microscope image of the Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the embodiment of the invention, and FIG. b is a corresponding transmission electron microscope XPS line scanning element analysis image.
FIG. 6A is a spherical aberration electron microscope image of the Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the example of the present invention, FIG. b is a Fourier image of the catalyst, FIG. c is an atomic image intensity distribution diagram shown along the arrow in a, and FIG. d is an enlarged view of the matrix mark region of FIG. a and a crystal model corresponding to the [220] crystal band axis projection.
FIG. 7 is a two-dimensional differential charge map of Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the examples of the present invention.
FIG. 8 is a graph showing the adsorption configuration of acetylene and ethylene on the surface of a Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the embodiment of the invention, wherein the graph a shows the adsorption configuration of acetylene on the surface of the catalyst, and the graph b shows the adsorption configuration of ethylene on the surface of the catalyst.
FIG. 9 is a graph showing the density of states of the Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the example of the present invention.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which specific embodiments are shown. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
Ni-Cu-Fe-Ga medium entropy intermetallic compound catalyst
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Cu-Fe-Ga, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、1.35 g Fe(NO3)3·9H2O、1.39 g Ga(NO3)3·9H2O、13.68 g Mg(NO3)2·6H2O( and 5.00 g Al (NO 3)3·9H2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, the molar ratio of Ni, cu, fe, ga, mg, al ions is 1:1:1:1:16:4; 4.24 g Na 2CO3 powder is dissolved in 100 mL ultrapure water for ultrasonic dispersion to obtain a precipitator, and 20.00 g NaOH powder is dissolved in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator.
(2) Dissolving 4.24 g Na 2CO3 powder in 100 mL ultrapure water for ultrasonic dispersion to obtain a precipitator; the 20.00 g NaOH powder was dissolved in 200 mL ultrapure water and dispersed by ultrasonic to obtain a pH adjuster. Transferring the precipitant into a 500mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 140 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 0.8 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass-green blocky solid Ni/Cu/Fe/Ga/Mg/Al six-element LDH material is obtained, and the sign is X5;
(3) And (3) reducing the Ni/Cu/Fe/Ga/Mg/Al six-element LDH material X5 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Cu-Fe-Ga medium entropy intermetallic compound catalyst which is marked as X5-900-4.
Example 2
Ni-Co-Fe-Ga medium entropy intermetallic compound catalyst
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Co-Fe-Ga, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、1.35 g Fe(NO3)3·9H2O、1.39 g Ga(NO3)3·9H2O、13.68g Mg(NO3)2·6H2O and 5.00 g Al (NO 3)3·9H2 O dissolved in 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, co, fe, ga, mg, al ions of 1:1:1:1:16:4;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 140 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 0.8 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass yellow blocky solid Ni/Co/Fe/Ga/Mg/Al six-element LDH material is obtained, and the mixture is marked as X6;
(3) And (3) reducing the Ni/Co/Fe/Ga/Mg/Al six-element LDH material X6 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Fe-Ga medium entropy intermetallic compound catalyst which is marked as X6-900-4.
Example 3
Ni-Co-Cu-Ga medium entropy intermetallic compound catalyst
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Co-Cu-Ga, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、1.39 g Ga(NO3)3·9H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, co, cu, ga, mg, al ions of 1:1:1:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 140 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 0.8 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that an off-white blocky solid Ni/Co/Cu/Ga/Mg/Al six-element LDH material is obtained, and the mark is X7;
(3) And (3) reducing the Ni/Co/Cu/Ga/Mg/Al six-element LDH material X7 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Cu-Ga medium entropy intermetallic compound catalyst which is marked as X7-900-4.
Example 4
Entropy intermetallic compound catalyst In Ni-Cu-Fe-In
The embodiment provides a preparation method of an entropy intermetallic compound catalyst In Ni-Cu-Fe-In, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、1.35 g Fe(NO3)3·9H2O、1.36 g In(NO3)3·9H2O、13.68 g Mg(NO3)2·6H2O and 5.00 g Al (NO 3)3·9H2 O dissolved in 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, cu, fe, in, mg, al ions of 1:1:1:1:16:4;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 160 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.2 mL/min, so that the pH of a reaction system In a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass-green blocky solid Ni/Cu/Fe/In/Mg/Al six-element LDH material is obtained, and the sign is X8;
(3) And (2) reducing the Ni/Cu/Fe/In/Mg/Al six-element LDH material X8 prepared In the step (2) by 4H In H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Cu-Fe-In entropy intermetallic compound catalyst which is marked as X8-900-4.
Example 5
Entropy intermetallic compound catalyst In Ni-Co-Fe-In
The embodiment provides a preparation method of an entropy intermetallic compound catalyst In Ni-Co-Fe-In, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、1.35 g Fe(NO3)3·9H2O、1.36 g In(NO3)3·9H2O、13.68g Mg(NO3)2·6H2O and 5.00 g Al (NO 3)3·9H2 O dissolved in 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, co, fe, in, mg, al ions of 1:1:1:1:16:4;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 160 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.2 mL/min, so that the pH of a reaction system In a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass yellow blocky solid Ni/Co/Fe/In/Mg/Al six-element LDH material is obtained, and the mixture is marked as X9;
(3) And (2) reducing the Ni/Co/Fe/In/Mg/Al six-element LDH material X9 prepared In the step (2) by 4H In H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Fe-In entropy intermetallic compound catalyst which is marked as X9-900-4.
Example 6
Entropy intermetallic compound catalyst In Ni-Co-Cu-In
The embodiment provides a preparation method of an entropy intermetallic compound catalyst In Ni-Co-Cu-In, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、1.36 g In(NO3)3·9H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, co, cu, in, mg, al ions of 1:1:1:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 160 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.2 mL/min, so that the pH of a reaction system In a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that an off-white blocky solid Ni/Co/Cu/In/Mg/Al six-element LDH material is obtained, and the mark is X10;
(3) And (2) reducing the Ni/Co/Cu/In/Mg/Al six-element LDH material X10 prepared In the step (2) by 4H In H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Cu-In entropy intermetallic compound catalyst which is marked as X10-900-4.
Example 7
Entropy intermetallic compound catalyst in Ni-Cu-Fe-Zn
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Cu-Fe-Zn, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、1.35 g Fe(NO3)3·9H2O、0.99 g Zn(NO3)2·6H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, cu, fe, zn, mg, al ions of 1:1:1:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.9 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.1 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass-green blocky solid Ni/Cu/Fe/Zn/Mg/Al six-element LDH material is obtained, and the sign is X11;
(3) And (3) reducing the Ni/Cu/Fe/Zn/Mg/Al six-element LDH material X11 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Cu-Fe-Zn entropy intermetallic compound catalyst which is marked as X11-900-4.
Example 8
Entropy intermetallic compound catalyst in Ni-Co-Fe-Zn
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Co-Fe-Zn, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、1.35 g Fe(NO3)3·9H2O、0.99 g Zn(NO3)2·6H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, co, fe, zn, mg, al ions of 1:1:1:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.9 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.1 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass yellow blocky solid Ni/Co/Fe/Zn/Mg/Al six-element LDH material is obtained, and the mixture is marked as X12;
(3) And (2) reducing the Ni/Co/Fe/Zn/Mg/Al six-element LDH material X12 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Fe-Zn entropy intermetallic compound catalyst which is marked as X12-900-4.
Example 9
Entropy intermetallic compound catalyst in Ni-Co-Cu-Zn
The embodiment provides a preparation method of an entropy intermetallic compound catalyst in Ni-Co-Cu-Zn, which specifically comprises the following steps:
(1) 0.97 g Ni(NO3)2·6H2O、0.97 g Co(NO3)2·6H2O、0.81 g Cu(NO3)2·3H2O、0.99 g Zn(NO3)2·6H2O、12.00 g Mg(NO3)2·6H2O and 7.50: 7.50 g Al (NO 3)3·9H2 O dissolved in 100: 100mL ultrapure water and dispersed ultrasonically, recorded as mixed metal nitrate solution, the molar ratio of Ni, co, cu, zn, mg, al ions is 1:1:1:1:14:6;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.9 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.1 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that an off-white blocky solid Ni/Co/Cu/Zn/Mg/Al six-element LDH material is obtained, and the mark is X13;
(3) And (3) reducing the Ni/Co/Cu/Zn/Mg/Al six-element LDH material X13 prepared in the step (2) by 4H in H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Co-Cu-Zn medium entropy intermetallic compound catalyst which is marked as X13-900-4.
Comparative examples 1 to 3
Ni 3 Ga intermetallic compound catalyst
The preparation of the Ni 3 Ga intermetallic compound catalyst comprises the following steps:
(1) 2.91 g Ni(NO3)2·6H2O、1.39 g Ga(NO3)3·9H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100 mL ultrapure water and dispersed ultrasonically, recorded as mixed metal nitrate solution, the molar ratio of Ni, ga, mg, al ions is 3:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100 mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 140 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.8 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.0 mL/min, the pH of a reaction system in a three-neck flask is enabled to be constant at 10.0+/-0.1, after the material feeding is completed, continuous and vigorous stirring is continued at the synthesis temperature of 65 ℃ for 16 h, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that the green massive solid Ni/Ga/Mg/Al quaternary LDH material is obtained, and the mark is X1.
(3) The prepared X1 is reduced for 2H, 4H and 6H respectively in H 2/N2 atmosphere (volume ratio is 1:4) at 900 ℃ to obtain Ni 3 Ga binary intermetallic compound catalysts which are respectively marked as X1-900-2, X1-900-4 and X1-900-6.
Comparative examples 4 to 6
Ni 3 In intermetallic compound catalyst
The preparation of the Ni 3 In intermetallic compound catalyst comprises the following steps:
(1) 2.91 g Ni(NO3)2·6H2O、1.36 g In(NO3)3·9H2O、12.82 g Mg(NO3)2·6H2O and 6.25: 6.25 g Al (NO 3)3·9H2 O dissolved in 100: 100 mL ultrapure water and dispersed ultrasonically, recorded as mixed metal nitrate solution, the molar ratio of Ni, in, mg, al ions is 3:1:15:5;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 160 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.2 mL/min, the pH of a reaction system In a three-neck flask is enabled to be constant at 10.0+/-0.1, after the material feeding is completed, continuous and vigorous stirring is continued at 65 ℃ for 16 h, then vacuum filtration is carried out, the pH is washed for multiple times to be neutral, and the green massive solid Ni/In/Mg/Al quaternary LDH material is obtained, and is marked as X2.
(3) And (3) reducing the X2 prepared In the step (2) In H 2/N2 atmosphere (volume ratio is 1:4) at 900 ℃ for 2H, 4H and 6H respectively to obtain Ni 3 In binary intermetallic compound catalysts which are respectively marked as X2-900-2, X2-900-4 and X2-900-6.
Comparative examples 7 to 9
Ni 3 Zn intermetallic compound catalyst
The preparation of the Ni 3 Zn intermetallic compound catalyst comprises the following steps:
(1) 2.91 g Ni(NO3)2·6H2O、0.99 g Zn(NO3)2·6H2O、12.00 g Mg(NO3)2·6H2O and 7.50 g Al (NO 3)3·9H2 O dissolved in 100 mL ultrapure water and dispersed by ultrasonic, recorded as mixed metal nitrate solution, the mol ratio of Ni, zn, mg, al ions is 3:1:14:6;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.9 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.1 mL/min, the pH of a reaction system in a three-neck flask is enabled to be constant at 10.0+/-0.1, after the material feeding is completed, continuous and vigorous stirring is continued at 65 ℃ for 16 h, then vacuum filtration is carried out, the pH is washed for multiple times to be neutral, and the green massive solid Ni/Zn/Mg/Al quaternary LDH material is obtained, and is marked as X3.
(3) And (3) reducing X3 prepared in the step (2) in H 2/N2 atmosphere (volume ratio 1:4) at 900 ℃ for 2, 4 and 6H respectively to obtain Ni 3 Zn binary intermetallic compound catalysts which are respectively marked as X3-900-2, X3-900-4 and X3-900-6.
Comparative example 10
NiFe 2 Ga intermetallic compound catalyst
(1) 0.97 g Ni(NO3)2·6H2O、2.70 g Fe(NO3)3·9H2O、1.39 g Ga(NO3)3·9H2O、13.68g Mg(NO3)2·6H2O And 5.00 g Al (NO 3)3·9H2 O dissolved in 100 mL ultrapure water and dispersed ultrasonically, noted as mixed metal nitrate solution, with a molar ratio of Ni, fe, in, mg, al ions of 1:2:1:16:4;
(2) Dissolving 4.24 g Na 2CO3 powder in 100mL ultrapure water for ultrasonic dispersion to obtain a precipitator; dissolving 20.00 g NaOH powder in 200 mL ultrapure water for ultrasonic dispersion to obtain a pH regulator;
Transferring the precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment of 1 h, then dropwise adding the mixed metal nitrate solution in the step (1) under the condition of the rotating speed of 160 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the flow rate is controlled to be 1.2 mL/min, so that the pH of a reaction system in a three-neck flask is constantly 10.0+/-0.1, after the material feeding is finished, the mixture is continuously and vigorously stirred for 16 h at the synthesis temperature of 65 ℃, then vacuum filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a grass yellow massive solid Ni/Fe/Ga/Mg/Al five-element LDH material is obtained, and the mixture is marked as X4;
(3) And (2) reducing the Ni/Fe/Ga/Mg/Al quinary LDH material X4 prepared In the step (2) by 4H In H 2/N2 atmosphere (volume ratio of 1:4) at 900 ℃ to obtain the Ni-Fe-In intermetallic compound catalyst which is marked as X4-900-4.
Characterization of the catalyst: FIG. 1 is a schematic structural diagram of the above-prepared intermediate entropy alloy intermetallic compound catalysts X5-900-4, X8-900-4 and X11-900-4, and it can be seen that the design concept of the intermediate entropy alloy intermetallic compound catalysts is to replace two Ni sites of Ni 3 M parent metal with active components M1 and M2. The XRD spectrum of the Ni-Cu-Fe-Ga intermediate alloy catalyst X5-900-4 prepared in example 1 is shown in figure 2, and it can be seen that the intermediate entropy intermetallic compound synthesized by the method has an obvious crystal structure, the diffraction intensity of the (111) crystal face is highest, and the distribution of the intermediate entropy intermetallic compound on the surface of the intermediate entropy alloy particle is the most. The transmission electron microscope image of the Ni-Cu-Fe-Ga intermediate alloy catalyst X5-900-4 prepared in the example 1 is shown in figure 3, and it can be seen that the intermediate alloy catalyst synthesized by the invention has obvious lattice fringes, and the XRD result of figure 2, namely the obvious crystal structure of the synthesized catalyst, is also verified. As shown in FIG. 4, elemental analysis was performed on the Ni-Cu-Fe-Ga medium entropy alloy intermetallic compound catalyst X5-900-4 obtained in example 1, the element Ni, cu, fe, ga is found to be evenly distributed, which indicates that a Ni-Cu-Fe-Ga quaternary alloy crystal phase is formed. In FIG. 5, the graph a is a transmission electron microscope graph of the Ni-Cu-Fe-Ga catalyst X5-900-4, and the graph b is a corresponding transmission electron microscope XPS line scanning element analysis graph, and it can be seen from the graph that elements Ni, cu, fe, ga are uniformly distributed, and the result is consistent with that of FIG. 4.
The characterization by a spherical aberration electron microscope is continued, and the result is shown in fig. 6, wherein the lattice spacing in the arrow direction in fig. a is 0.205 nm, which corresponds to the (111) plane of the medium entropy alloy Ni-Cu-Fe-Ga. The atomic radii of the elements Ni, cu and Fe are close, so that after the guest metals Cu and Fe replace Ni sites in the parent metal Ni 3 Ga, the lattice spacing is not changed significantly; FIG. 6D further shows that the atomic arrangement of the catalyst particles is highly matched with the results obtained by the theoretical calculation and simulation of the density functional of Ni-Cu-Fe-Ga, which shows that the sites of four metal elements are orderly arranged to form a quadruple site structure of Ni-Cu-Fe-Ga; according to a corresponding XPS line scan analysis chart, the elements Ni, cu, fe, ga in the Ni-Cu-Fe-Ga medium entropy alloy intermetallic compound catalyst are uniformly distributed, and the content ratio of the elements Ni, cu, fe, ga is close to 1:1:1:1.
The charge analysis is carried out on the entropy alloy intermetallic compound catalyst X5-900-4 in Ni-Cu-Fe-Ga, and the result is shown in figure 7, wherein the charge is concentrated and distributed at the center of the three-tooth sites of Fe, ni and Cu, which shows that the transfer of electrons from inert metal Ga to active metals Fe, ni and Cu occurs, and a Ni-Cu-Fe-Ga quadruple site structure rich in electrons Ni, fe and Cu and with isolated electron deficiency Ga is formed.
FIG. 8 is a graph showing the adsorption configuration of acetylene and ethylene on the surface of a Ni-Cu-Fe-Ga catalyst X5-900-4 prepared in the embodiment of the invention, wherein the graph a shows the adsorption configuration of acetylene on the surface of the catalyst, and the graph b shows the adsorption configuration of ethylene on the surface of the catalyst.
The density functional theory calculation shows that the multidentate diamond-shaped sites formed by Ni-M1-M2-M3 are favorable for acetylene adsorption (the adsorption energy is-2.14 eV), and the larger acetylene adsorption energy is favorable for acetylene adsorption; ethylene generated by selective hydrogenation of acetylene can be preferentially adsorbed on Ni sites to form pi-type adsorption (the adsorption energy is-0.33 eV), and the smaller ethylene adsorption energy is beneficial to desorption of ethylene.
By plotting the state density of the entropy alloy intermetallic compound in ni—cu—fe—ga, as shown in fig. 9, the modification effect of the inert metal Ga on Ni, fe, cu active sites resulted from hybridization between the d-orbitals of Ni, fe, cu and Ga sp orbitals in the vicinity of-3.5 eV. The method shows that the intermediate entropy alloy intermetallic compound has more complex element components and more optimized electronic structure, and is not limited to the two-site coordination of the conventional bimetallic catalyst, but the coordination of four element site structures is consistent.
Catalyst acetylene hydrogenation Performance evaluation
Performing acetylene selective hydrogenation reaction activity evaluation by adopting the Ni-M1-M2-M3 medium entropy intermetallic compound catalyst prepared in the examples 1-9 and the binary Ni-based catalyst prepared in the comparative examples 1-10; the acetylene hydrogenation performance evaluation was performed on a Beijing Wanlon and science and technology Co., ltd ZKJC-RJ-X system, in which:
the components in the reactants and products were analyzed on-line using a 4-channel micro-chromatography micro GC 3000 (INFICON company, usa).
The hydrogen and nitrogen were analyzed using molecular sieve columns, acetylene was using Plot-U columns, ethylene and ethane were analyzed using alumina columns, very low amounts of C4 components in the feed gas were analyzed using OV-1 capillary chromatography columns, the detectors were thermal conductivity cell detectors (Thermal Conductivity Detector, TCD) and the carrier gases were Ar and He.
Evaluation conditions: the total flow of the inlet gas is 100 mL/min, the raw material gas is 0.5% of C 2H2, 50.0% of C 2H4, 10.0% of H 2, and the rest gas is N 2; the reaction temperature is 20-130 ℃ and the pressure is normal; the catalyst loading was 100 mg.
100 Mg catalyst samples are weighed, evenly mixed with 10 times of quartz sand by mass and then filled in a constant temperature area in a stainless steel reaction tube. After the catalyst is filled, the reaction system is subjected to leak detection, a certain pressure N 2 (such as 10 bar) is introduced into the reaction system, the pressure can be kept unchanged, the reaction system is good in tightness, and an evaluation experiment can be carried out.
Setting the flow rate of nitrogen to be 20 sccm (Standard cube CENTIMETER PER Minute), and heating to a reduction temperature; then closing the nitrogen, setting the hydrogen flow to be 20 sccm, and closing the hydrogen after reducing for a certain time; setting the flow of nitrogen to be 20 sccm, cooling to the reaction temperature, and setting the pressure required by the reaction. After the reaction conditions are stable, the flow rate of each reaction component is set, and a Furnace six-way valve is cut into a bypass, so that the mixed gas directly enters the chromatograph to detect the concentration of each component before the reaction. After stabilization, the Furnace six-way valve was switched back into the reaction tube to start the reaction, and the outlet gas of the reaction tube was subjected to on-line chromatographic detection.
Acetylene conversion by testing the binary Ni-based catalysts and Ni-M1-M2-M3 medium entropy intermetallic compound catalysts prepared in comparative examples 1-10 and examples 1-9Ethylene selectivityYield from ethyleneTo evaluate the catalytic performance of the catalyst on the reaction of preparing ethylene by acetylene selective hydrogenation, wherein:
the test results are shown in tables 1 to 3.
TABLE 1 catalyst acetylene hydrogenation conversion (%)
TABLE 2 catalyst acetylene hydrogenation ethylene Selectivity (%)
TABLE 3 catalyst acetylene hydrogenation ethylene yield (%)
As can be seen from the results shown in tables 1 to 3, under the conditions that the reaction pressure is normal pressure and the raw materials are rich in ethylene, compared with a binary Ni-based catalyst and a NiFe 2 Ga intermetallic compound catalyst with the same components of M1 and M2, the catalyst for the entropy intermetallic compound in the Ni-M1-M2-M3 has obviously improved ethylene selectivity and yield, and the catalyst for the entropy intermetallic compound in the Ni-M1-M2-M3 prepared by the embodiment has extremely high ethylene selectivity in the range of 20-130 ℃ and can simultaneously obtain higher acetylene conversion rate and ethylene selectivity when the temperature reaches 100 ℃ or above. The method shows that compared with a binary Ni-based catalyst, the entropy intermetallic compound catalyst in Ni-M1-M2-M3 prepared by adopting the technical scheme of the invention can obviously improve the acetylene conversion rate, the ethylene selectivity and the ethylene yield.
Evaluation of catalyst acetylene hydrogenation stability
The catalyst X5-900-4 prepared in example 1 was randomly selected, and the stability of the catalyst was evaluated at 110℃according to the catalyst performance test method of the catalyst acetylene hydrogenation performance evaluation experiment described above,And (3) withThe data results are shown in table 4.
Table 4 X5-900-4 catalyst evaluation of acetylene hydrogenation stability
As can be seen from the results shown in Table 4, the catalyst X5-900-4 prepared in example 1 was still maintained at an acetylene conversion of 97% or more, an ethylene selectivity of 97% or more and a propylene selectivity of 94% or more after 48 hours of reaction evaluation, indicating good stability.
Evaluation of catalyst propyne hydrogenation stability
The activity evaluation of the selective hydrogenation reaction of propyne is carried out by adopting the Ni-Cu-Fe-Ga intermediate entropy intermetallic compound catalyst X5-900-4 prepared in the example 1; propyne hydrogenation performance evaluation was performed on a Beijing Wanlon and science and technology company ZKJC-RJ-X system, in which:
The components in the reactants and products were analyzed on-line using a 4-channel Micro GC Fusion (INFICON company, germany). The hydrogen and nitrogen were molecular sieve columns, the propyne was Rt-U-Bond columns, the propylene and propane were AluminaNa 2SO4 columns, the detector was a thermal conductivity cell detector (Thermal Conductivity Detector, TCD) and the carrier gas was He.
Evaluation conditions: the total flow of the inlet gas is 100 mL/min, the raw material gas is 1.0% of C 3H4, 10.0% of C 3H6, 5.0% of H 2, and the rest gas is N 2; the reaction temperature is 110 ℃ and the pressure is normal; the catalyst loading was 100 mg.
100 Mg catalyst samples are weighed, evenly mixed with 10 times of quartz sand by mass and then filled in a constant temperature area in a stainless steel reaction tube. After the catalyst is filled, the reaction system is subjected to leak detection, a certain pressure N 2 (such as 10 bar) is introduced into the reaction system, the pressure can be kept unchanged, the reaction system is good in tightness, and an evaluation experiment can be carried out.
Setting the flow rate of nitrogen to be 20 sccm (Standard cube CENTIMETER PER Minute), and heating to a reduction temperature; then closing the nitrogen, setting the hydrogen flow to be 20 sccm, and closing the hydrogen after reducing for a certain time; setting the flow of nitrogen to be 20 sccm, cooling to the reaction temperature, and setting the pressure required by the reaction. After the reaction conditions are stable, the flow rate of each reaction component is set, and a Furnace six-way valve is cut into a bypass, so that the mixed gas directly enters the chromatograph to detect the concentration of each component before the reaction. After stabilization, the Furnace six-way valve was switched back into the reaction tube to start the reaction, and the outlet gas of the reaction tube was subjected to on-line chromatographic detection.
The stability of the X5-900-4 catalyst prepared in example 1 was evaluated to obtain propyne conversionPropylene selectivityYield from propyleneWherein:
The results are shown in Table 5.
Evaluation of the hydrogenation stability of propyne in the catalyst of Table 5, X5-900-4
As shown in Table 5, the result shows that the catalyst X5-900-4 prepared in the examples still maintains the propyne conversion rate above 97% and the propylene selectivity above 97% and the propylene yield above 95% after 48 hours of reaction evaluation, which shows that the catalyst has good stability.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. The catalyst is characterized In that the catalyst takes Mg-Al oxide as a carrier, active metal components M1 and M2 are selected from one of Fe, co and Cu, M1 and M2 are different, and inert metal component M3 is selected from one of Ga, in and Zn; four metals in the catalyst jointly form Ni-M1-M2-M3 multi-tooth diamond active sites, wherein the local electron cloud structures of the active metals Ni, M1 and M2 are regulated and controlled by low electronegativity inert metal M3, and a Ni-M1-M2-M3 quadruple site structure rich in electrons Ni, M1 and M2 and lacking electrons M3 in isolation is formed;
The preparation method of the Ni-M1-M2-M3 medium entropy intermetallic compound catalyst comprises the following steps:
(1) Preparing nitrate of Ni, M1, M2, M3, mg and Al into mixed metal nitrate solution, and preparing a Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M by adopting a coprecipitation method; in the mixed metal nitrate solution, the molar ratio of Ni, M1, M2, M3, mg and Al ions is 1 (0.95-1.05): (0.95-1.05): (14-17): (4-6);
(2) And (3) carrying out vacuum suction filtration, washing and drying on the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M obtained in the step (1), and then carrying out thermal reduction treatment to obtain the intermediate entropy intermetallic compound catalyst.
2. A method for preparing the catalyst for entropy intermetallic compounds in Ni-M1-M2-M3 as claimed in claim 1, comprising the steps of:
(1) Preparing nitrate of Ni, M1, M2, M3, mg and Al into mixed metal nitrate solution, and preparing a Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M by adopting a coprecipitation method;
(2) Carrying out vacuum suction filtration, washing and drying on the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M obtained in the step (1), and then carrying out thermal reduction treatment to obtain an entropy intermetallic compound catalyst;
Wherein M1 and M2 are selected from one of Fe, co and Cu, M1 and M2 are different, and M3 is selected from one of Ga, in and Zn; in the step (1), in the mixed metal nitrate solution, the molar ratio of Ni, M1, M2, M3, mg and Al ions is 1 (0.95-1.05): (0.95-1.05): (14-17): (4-6).
3. The method for preparing an entropy intermetallic compound catalyst in Ni-M1-M2-M3 according to claim 2, wherein in step (1), the ion concentration of Ni in the mixed metal nitrate solution is 0.03 to 0.05mol/L.
4. The method for preparing an entropy intermetallic compound catalyst in Ni-M1-M2-M3 according to claim 2, wherein the nitrate salt of Ni, fe, co, cu, ga, in, zn, mg, al in step (1) is nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, copper nitrate trihydrate, gallium nitrate nonahydrate, indium nitrate nonahydrate, zinc nitrate hexahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, respectively.
5. The method for preparing an entropy intermetallic compound catalyst in Ni-M1-M2-M3 according to claim 2, wherein in the step (1), a mixed metal nitrate solution and a pH regulator are added to the precipitant simultaneously under stirring, the temperature of the reaction system is maintained at 60-70 ℃, and the pH value of the reaction system is controlled at 10+ -1; after the addition is finished, stirring and reacting for 14-18 h, and finally filtering, washing and drying to obtain the Ni/M1/M2/M3/Mg/Al six-membered layered double hydroxide material M.
6. The method for preparing an entropy intermetallic compound catalyst in Ni-M1-M2-M3 according to claim 5, wherein the addition rate of the mixed metal nitrate solution is controlled to be 0.9±0.2mL/min.
7. The method for preparing the catalyst for entropy intermetallic compounds in Ni-M1-M2-M3 according to claim 5, wherein the precipitant is one selected from sodium carbonate solution, ammonia water, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution; the pH regulator is selected from one of sodium bicarbonate solution, potassium hydroxide solution and sodium hydroxide solution.
8. The method for preparing an entropy intermetallic compound catalyst in Ni-M1-M2-M3 according to claim 2, wherein in step (2), the thermal reduction temperature is 600-1000 ℃, the reduction time is 2-6H, and the reducing gas is H 2/N2 gas mixture.
9. Use of the Ni-M1-M2-M3 medium entropy intermetallic catalyst of claim 1 or the Ni-M1-M2-M3 medium entropy intermetallic catalyst prepared according to any of claims 2-8 for the selective hydrogenation of acetylene to ethylene or propyne to propylene.
10. The use according to claim 9, wherein the hydrogenation reaction conditions are: the temperature is 20-130 ℃ and the pressure is normal.
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CN111617772A (en) * 2020-06-03 2020-09-04 华东理工大学 Supported Ni-Ga-Pd catalyst and preparation method and application thereof

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