CN115646492A - CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof - Google Patents

CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof Download PDF

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CN115646492A
CN115646492A CN202211328306.0A CN202211328306A CN115646492A CN 115646492 A CN115646492 A CN 115646492A CN 202211328306 A CN202211328306 A CN 202211328306A CN 115646492 A CN115646492 A CN 115646492A
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苗文康
郝荣辉
李倩倩
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University of Shanghai for Science and Technology
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Abstract

The invention discloses CoFe @ Fe with a core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof, wherein the prepared catalyst core is CoFe alloy with the diameter of 20nm, and the shell is Fe with the thickness of 2nm 3 O 4 The carbon carrier is uniformly loaded on the defect-rich carbon carrier, and the phenomenon of sintering and agglomeration does not occur. In addition, the material of the invention is used as CO 2 The catalyst shows excellent catalytic activity when being hydrogenated, and CO is at 450 DEG C 2 The conversion rate is 30 percent, the CO selectivity is 99 percent, and the material is pollution-free and easy to synthesize, and can be well applied to the technical fields of energy materials and the like.

Description

CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention relates to CO 2 A hydrogenation catalyst and a preparation and application method thereof, in particular to a defect-rich carbon supported CoFe @ Fe with a core-shell structure 3 O 4 An alloy catalyst and a preparation method thereof.
Background
The fossil energy brings huge energy for the survival and development of human beings, and the occupancy rate of the fossil energy in a global energy system is as high as 78.9 percent by 2019, so that a large amount of fossil energy is burnt to cause energy exhaustion, and CO discharged into the atmosphere 2 The gases cause a severe greenhouse effect. Thus, catalytic conversion of CO 2 The method is an effective measure for solving energy and environmental crisis for clean energy. However, CO 2 Is a non-polar linear molecule with short carbon-oxygen bond distance, which makes CO 2 The molecules are very stable and direct conversion becomes difficult. By introduction of H 2 Can reduce Gibbs free energy of the whole reaction and lead the reaction to occur under a milder condition. CO2 2 Hydrogenation can obtain a plurality of products, such as low carbon alcohol, low carbon olefin, dimethyl ether, low carbonic acid, methane, carbon monoxide and the like, wherein the methane and the carbon monoxide can be obtained by reaction under normal pressure, and the carbon monoxide and the hydrogen can also be used as synthesis gas to synthesize high value-added chemicals by subsequent Fischer-Tropsch reaction, which is widely applied in industry, so that CO can be widely used 2 The reaction of hydrogenation to carbon monoxide (reverse water gas shift reaction) has important research value.
Noble metal catalysts, e.g. platinum based catalysts, in CO 2 Has higher reactivity in hydrogenation reaction, but often cannot simultaneously have high CO 2 Conversion and high CO selectivity (especially at high reaction temperatures), and are limited by the cost of the noble metal, which limits its widespread use. Thus, in recent years researchers have turned more attention to the class of non-noble metal catalysts, whose activity and selectivity can reach or even exceed the level of noble metal catalysts through rational structure and composition design. Binary non-noble metal CoFe alloy is considered as a promising CO 2 Hydrogenation catalysts, however, binary CoFe alloys still suffer from a number of problems, such as reactant gases (CO) 2 And H 2 ) Insufficient adsorption and activation capability, sintering and agglomeration and the like.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a CoFe @ Fe core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, process for its preparation and its use, coFe @ Fe 3 O 4 The alloy particles are uniformly loaded on the defect-rich carbon carrier, and sintering agglomeration does not occurLike, let CoFe @ Fe 3 O 4 Alloy composite material in CO 2 High activity and stability in hydrogenation reaction.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Preparation method of hydrogenation catalyst, using CoFe 2 O 4 And g-C 3 N 4 As a precursor material, preparing a CoFe alloy with the core diameter of 5-25nm and the shell thickness of 1-5nm, which is loaded on a defect-rich carbon carrier, by adopting a heat treatment method 3 O 4 As a catalyst material for CO 2 Catalyst material for hydrogenation reaction.
Preferably, fe with a core diameter of 20nm and a shell thickness of 2nm supported on a defect-rich carbon support is prepared 3 O 4 The catalyst material of (1).
Preferably, coFe @ Fe with core-shell structure provided by the invention 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps:
step 1: preparing Co by wet chemical method x Fe y O 4 The molar ratio of CoFe element prepared according to the target is (1-2): (2-1), wherein x is 1 to 2, y is 1 to 2;
step 2: preparation of g-C by thermal polymerization 3 N 4 Ultrasonic stripping is carried out on the mixture with the ultrasonic power of 100-500W, supernatant fluid is obtained by centrifugation, and layered g-C is prepared 3 N 4 ；
And 3, step 3: co to be prepared in said step 1 x Fe y O 4 Supporting g-C in the layer form prepared in said step 2 3 N 4 To make Co x Fe y O 4 A loading of not more than 30wt% to obtain g-C 3 N 4 /Co x Fe y O 4 A composite material;
and 4, step 4: for g-C prepared in said step 3 3 N 4 /Co x Fe y O 4 The composite material is subjected to an annealing treatment,the annealing temperature is 300-600 ℃, and the mixture is cooled to the room temperature to obtain the defect-rich carbon supported CoFe @ Fe with the core-shell structure 3 O 4 An alloy catalyst material.
Preferably, in the step 1, no more than 2mmol of cobalt acetylacetonate and no more than 2mmol of iron acetylacetonate are weighed and ultrasonically dispersed in triethylene glycol; heating the mixed solution to be not higher than 110 ℃, and preserving the heat for at least 30min; then raising the temperature to not higher than 250 ℃ and preserving the heat for at least 60min; cooling to room temperature, washing with ethyl acetate, and lyophilizing to obtain Co x Fe y O 4 。
Preferably, in the step 2, at least 10g of urea is weighed and placed in a 50mL crucible, the temperature is raised to be not lower than 550 ℃ at the temperature rise speed of not lower than 2.3 ℃/min, the temperature is kept for at least 4 hours, and thermal polymerization is carried out; then, carrying out ultrasonic stripping on the product, wherein the ultrasonic power is 100-500W; then taking supernatant fluid for freeze-drying to obtain the lamellar g-C 3 N 4 。
Preferably, in step 3 above, at least 100mg of lamellar g-C are taken 3 N 4 Ultrasonically dispersing in deionized water; then 5-30mg of Co is added x Fe y O 4 Performing ultrasonic treatment for 1h; freeze drying to obtain g-C 3 N 4 /Co x Fe y O 4 A composite material.
Preferably, in the above step 4, g-C is taken 3 N 4 /Co x Fe y O 4 Composite material of in CO 2 And H 2 Annealing in the mixed gas, and calculating according to the volume percentage content, H in the mixed gas 2 25-50vol% of CO 2 0-25vol%, ar as equilibrium gas, and 300-600 deg.C; coFe @ Fe with core-shell structure and capable of forming defect-rich carbon support after annealing 3 O 4 An alloy catalyst material.
CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 The hydrogenation catalyst utilizes the CoFe @ Fe with the core-shell structure 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst.
Preferably, having a core shellCoFe @ Fe of structure 3 O 4 Uniform size of nanoparticles, and CoFe @ Fe 3 O 4 The nanoparticles are uniformly distributed on the defect-rich carbon support to form a composite structure.
The invention relates to CoFe @ Fe with a core-shell structure 3 O 4 Alloy CO 2 Application of hydrogenation catalyst, namely CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalysts as CO 2 Catalyst material for hydrogenation reaction. The catalyst is used in CO2 hydrogenation reaction and has extremely high reaction activity and stability.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention relates to a defect-rich carbon supported CoFe @ Fe with a core-shell structure 3 O 4 The alloy catalyst has excellent shape structure, wherein the core is CoFe alloy, and the shell is Fe 3 O 4 ，CoFe@Fe 3 O 4 The size is uniform and evenly distributed on the carbon carrier rich in defects, and no agglomeration and sintering phenomena occur in the reaction process;
2. the invention relates to a defect-rich carbon supported CoFe @ Fe with a core-shell structure 3 O 4 Use of alloy catalyst in CO 2 In the catalytic reaction of hydrogenation, extremely high catalytic reaction activity and stability are shown due to the defect-rich carbon support and CoFe @ Fe 3 O 4 Respectively increase CO 2 And H 2 Adsorption and activation of (3);
3. the preparation method is simple in preparation process, low in cost and capable of realizing industrialization.
Drawings
FIG. 1 is an X-ray diffraction pattern of the materials synthesized in examples 1-4.
FIG. 2 is a transmission electron micrograph and an electron energy loss spectrum of example 1.
FIG. 3 is a selected area electron diffraction pattern of example 1.
FIG. 4 is a Raman diagram of example 1.
FIG. 5 is CO of examples 1 to 3 2 And (4) a hydrogenation reaction performance diagram.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1
In the embodiment, coFe @ Fe supported by defect-rich carbon and provided with core-shell structure 3 O 4 The preparation method of the alloy catalyst comprises the following steps:
step 1: ultrasonically dispersing 1mmol (256 mg) of cobalt acetylacetonate and 1mmol (353 mg) of iron acetylacetonate in triethylene glycol by a wet chemical method; heating the mixed solution to 110 ℃, and preserving the heat for 30min; then raising the temperature to 250 ℃ and preserving the heat for 60min; finally cooling to room temperature, centrifugally cleaning by ethyl acetate and freeze-drying to obtain a sample CoFeO 4 A precursor material;
and 2, step: adopting a thermal polymerization method, putting 10g of urea into a 50mL crucible, heating to 550 ℃ at the heating rate of 2.3 ℃/min, and preserving heat for 4h; then ultrasonic stripping is carried out, and the ultrasonic power is 300W; taking the supernatant, and freeze-drying to obtain lamellar g-C 3 N 4 ；
And step 3: taking 100mg of layers g-C 3 N 4 Ultrasonically dispersing in deionized water; 15mg of CoFeO obtained in step 1 were then added 4 Precursor material, ultrasonic processing for 1h; freeze drying to obtain g-C 3 N 4 /CoFeO 4 A composite material;
and 4, step 4: subjecting the material obtained in step 3 to CO 2 And H 2 Annealing in the mixed gas of H in the mixed gas 2 25vol% of CO 2 25vol%, ar as equilibrium gas, 450 ℃ as annealing temperature, and keeping the temperature for 1h; cooling to room temperature to obtain the defect-rich carbon supported CoFe @ Fe with the core-shell structure 3 O 4 An alloy catalyst material.
Example 2
This embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a preparation method of a Co catalyst material supported by defect-rich carbon and having a core-shell structure includes the following steps:
step 1: taking 1mmol (256 mg) of cobalt acetylacetonate and 0mmol (0 mg) of iron acetylacetonate, and ultrasonically dispersing the cobalt acetylacetonate and the 0mmol (0 mg) of iron acetylacetonate in triethylene glycol; heating the mixed solution to 110 ℃, and preserving the heat for 30min; then raising the temperature to 250 ℃ and preserving the heat for 60min; finally cooling to room temperature, centrifugally cleaning by ethyl acetate and freeze-drying to obtain a sample Co 3 O 4 ；
Step 2: in the same manner as in example 1, layered g-C was obtained 3 N 4 ；
And step 3: in the same manner as in example 1, g-C was obtained 3 N 4 /Co 3 O 4 A composite material;
and 4, step 4: different from the embodiment 1, the Co catalyst material which is supported by the defect-rich carbon and has a core-shell structure is obtained.
Example 3
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this example, a defect-rich carbon supported Fe with core-shell structure 3 O 4 The preparation method of the catalyst material comprises the following steps:
step 1: taking 0mmol (0 mg) of cobalt acetylacetonate and 1mmol (353 mg) of iron acetylacetonate, and ultrasonically dispersing the cobalt acetylacetonate and the iron acetylacetonate in triethylene glycol; heating the mixed solution to 110 ℃, and preserving the heat for 30min; then raising the temperature to 250 ℃ and preserving the heat for 60min; finally cooling to room temperature, centrifugally cleaning with ethyl acetate and freeze-drying to obtain a sample Fe 3 O 4 ；
Step 2: in the same manner as in example 1, layered g-C was obtained 3 N 4 ；
And step 3: in the same manner as in example 1, g-C was obtained 3 N 4 /Fe 3 O 4 A composite material;
and 4, step 4: in contrast to example 1, a defect-rich carbon-supported Fe with a core-shell structure was obtained 3 O 4 A catalyst material.
Example 4
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this example, a defect-rich carbon supported core shellCoFe @ Fe of structure 3 O 4 The preparation method of the alloy catalyst comprises the following steps:
step 1: as in example 1, a sample CoFeO was obtained 4 ；
Step 2: in the same manner as in example 1, layered g-C was obtained 3 N 4 ；
And step 3: in the same manner as in example 1, g-C was obtained 3 N 4 /CoFeO 4 A composite material;
and 4, step 4: subjecting the material obtained in step 3 to CO 2 And H 2 Annealing in the mixed gas of H in the mixed gas 2 50vol%, ar as equilibrium gas, 450 ℃ as annealing temperature, and 1h as heat preservation; cooling to room temperature to obtain the defect-rich carbon supported CoFe @ Fe with core-shell structure 3 O 4 An alloy catalyst material.
Example 5
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in the embodiment, the defect-rich carbon supported CoFe @ Fe with a core-shell structure 3 O 4 The preparation method of the alloy catalyst comprises the following steps:
step 1: 1mmol of cobalt acetylacetonate and 2mmol of iron acetylacetonate are ultrasonically dispersed in triethylene glycol by adopting a wet chemical method; heating the mixed solution to 110 ℃, and preserving the heat for 30min; then raising the temperature to 250 ℃ and preserving the heat for 60min; finally cooling to room temperature, centrifugally cleaning by ethyl acetate and freeze-drying to obtain a sample CoFeO 4 A precursor material;
step 2: in the same manner as in example 1, layered g-C was obtained 3 N 4 ；
And 3, step 3: in the same manner as in example 1, g-C was obtained 3 N 4 /CoFeO 4 A composite material;
and 4, step 4: as in example 1, a defect-rich carbon-supported CoFe @ Fe with core-shell structure was obtained 3 O 4 An alloy catalyst material.
Example 6
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in the embodiment, the defect-rich carbon supported CoFe @ Fe with a core-shell structure 3 O 4 The preparation method of the alloy catalyst comprises the following steps:
step 1: ultrasonically dispersing 2mmol of cobalt acetylacetonate and 1mmol of iron acetylacetonate in triethylene glycol by a wet chemical method; heating the mixed solution to 110 ℃, and preserving the heat for 30min; then raising the temperature to 250 ℃ and preserving the heat for 60min; finally cooling to room temperature, centrifugally cleaning by ethyl acetate and freeze-drying to obtain a sample CoFeO 4 A precursor material;
and 2, step: in the same manner as in example 1, layered g-C was obtained 3 N 4 ；
And step 3: in the same manner as in example 1, g-C was obtained 3 N 4 /CoFeO 4 A composite material;
and 4, step 4: as in example 1, a defect-rich carbon-supported CoFe @ Fe with core-shell structure was obtained 3 O 4 An alloy catalyst material.
Experimental test analysis:
characterization analysis of the material was performed:
1. the results of X-ray diffraction analysis of the materials of the above examples are shown in FIG. 1, and it can be seen that different products can be obtained for different CoFe ratios, and examples 1 to 4 correspond to CoFe @ Fe 3 O 4 Co simple substance, fe 3 O 4 And CoFe @ Fe 3 O 4 . The product obtained in example 1 was analyzed by a Transmission Electron Microscope (TEM) and an Electron Energy Loss Spectroscopy (EELS), and as a result, as shown in fig. 2, it can be seen that nanoparticles having a core-shell structure with a diameter of 25nm were distributed on a carbon support, wherein the thickness of the shell was 2nm, and further, the core-shell structure was subjected to composition analysis, and the EELSmapping and line scanning structure showed that the composition of the shell was iron oxide and the composition of the inner core was CoFe alloy. In order to further determine the phase structure of the material, selective electron diffraction (SAED) analysis was performed, and the results are shown in FIG. 3, wherein the material contains α -C and Fe 3 O 4 And CoFe alloys. Simultaneously, the material of the example 1 is subjected to Raman spectrum characterization, and the result is shown in figure 4,it can be seen that the ratio of the D peak to the G peak is 0.82, indicating that the carbon material contains a large number of defects which contribute to CO in the catalytic reaction 2 Adsorption and activation. It is clearly understood from the analysis combining XRD, TEM, EELS, SAED and Raman that the material synthesized in example 1 is a CoFe alloy with a core of 20nm diameter and a shell of 2nm thickness of Fe 3 O 4 ，CoFe@Fe 3 O 4 The size is uniform and evenly distributed on the defect-rich carbon carrier.
2. Evaluation of catalyst Performance:
CO was performed on the samples of examples 1-3 2 And (3) evaluating the hydrogenation performance, wherein the test method comprises the following steps: 20mg of catalyst was placed between two quartz wool layers in the center of a quartz tube (6 mm inner diameter), and the catalyst was exposed to a reaction gas (H) at normal pressure before the catalytic test 2 /CO 2 /Ar＝2.5/2.5/5mLmin -1 ,WHSV＝30000mLh -1 gcat -1 ) Pretreatment was carried out at 450 ℃ for 1h. The catalytic performance was then tested at different temperatures (250-500 ℃ C.) in the same reaction atmosphere and the product was analyzed using an on-line gas chromatograph (GC 7900 II, tian Mei, china) equipped with a TDX-01 column, a thermal conductivity detector and a flame ionization detector. The test results are shown in FIG. 5, and it can be seen that CoFe @ Fe is supported on the defect-rich carbon 3 O 4 Has the best catalytic activity, wherein CO 2 The conversion rate is 30 percent, the CO selectivity is 99 percent, and compared with the single element, the CO of the single element Co has poor catalytic performance 2 Conversion rate is only 5%, fe formed by single element 3 O 4 The conversion rate is 25%, but the CO selectivity is only 78%, and the comparison can obtain the double-element CoFe @ Fe 3 O 4 Has the best CO 2 Hydrogenation catalytic performance.
CoFe @ Fe with core-shell structure supported by defect-rich carbon as described in examples 1 and 4 to 6 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof, wherein the prepared catalyst core is CoFe alloy with the diameter of 20nm, and the shell is Fe with the thickness of 2nm 3 O 4 The carbon carrier is uniformly loaded on the defect-rich carbon carrier, and the phenomenon of sintering and agglomeration does not occur. In addition, the material of the invention is in the process ofIs CO 2 The catalyst shows excellent catalytic activity when being used as a hydrogenation catalyst, and CO is at 450 DEG C 2 The conversion rate is 30 percent, the CO selectivity is 99 percent, and the material is pollution-free and easy to synthesize, and can be well applied to the technical fields of energy materials and the like.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and all changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be made in the form of equivalent substitution, so long as the invention is in accordance with the purpose of the invention, and the invention shall fall within the protection scope of the present invention as long as the technical principle and the inventive concept of the present invention are not departed from the present invention.

Claims (10)

1. CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: with CoFe 2 O 4 And g-C 3 N 4 As a precursor material, preparing a CoFe alloy with the core diameter of 5-25nm and the shell thickness of 1-5nm, which is loaded on a defect-rich carbon carrier, by adopting a heat treatment method 3 O 4 As a catalyst material for CO 2 Catalyst material for hydrogenation reaction.
2. CoFe @ Fe with core-shell structure according to claim 2 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: preparation of CoFe alloy with 20nm core diameter and 2nm shell thickness supported on defect-rich carbon support 3 O 4 The catalyst material of (1).
3. CoFe @ Fe having a core-shell structure according to claim 1 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps:
step 1: preparing Co by wet chemical method x Fe y O 4 The molar ratio of CoFe element prepared according to the target is (1-2): (2-1) whereinx is 1-2, y is 1-2;
step 2: preparation of g-C by thermal polymerization 3 N 4 Ultrasonic peeling is carried out on the mixture, the ultrasonic power is 100-500W, supernatant fluid is obtained by centrifugation, and the lamellar g-C is prepared 3 N 4 ；
And step 3: co to be prepared in said step 1 x Fe y O 4 Supporting g-C in the layer form prepared in said step 2 3 N 4 To make Co x Fe y O 4 A loading of not more than 30wt% to obtain g-C 3 N 4 /Co x Fe y O 4 A composite material;
and 4, step 4: for g-C prepared in said step 3 3 N 4 /Co x Fe y O 4 Annealing the composite material at 300-600 ℃, and cooling to room temperature to obtain the defect-rich carbon-supported CoFe @ Fe with the core-shell structure 3 O 4 An alloy catalyst material.
4. CoFe @ Fe with core-shell structure according to claim 3 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: in the step 1, weighing not more than 2mmol of cobalt acetylacetonate and not more than 2mmol of iron acetylacetonate, and ultrasonically dispersing in triethylene glycol; heating the mixed solution to be not higher than 110 ℃, and preserving the heat for at least 30min; then raising the temperature to not higher than 250 ℃ and preserving the heat for at least 60min; cooling to room temperature, washing with ethyl acetate, and lyophilizing to obtain Co x Fe y O 4 。
5. CoFe @ Fe with core-shell structure according to claim 3 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: in the step 2, at least 10g of urea is weighed and placed in a 50mL crucible, the temperature is raised to be not lower than 550 ℃ at the heating rate of not lower than 2.3 ℃/min, the temperature is kept for at least 4h, and thermal polymerization reaction is carried out; then, carrying out ultrasonic stripping on the product, wherein the ultrasonic power is 100-500W; then taking supernatant fluid for freeze-drying to obtain the lamellar g-C 3 N 4 。
6. CoFe @ Fe with core-shell structure according to claim 3 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: in the above step 3, at least 100mg of lamellar g-C are taken 3 N 4 Ultrasonically dispersing in deionized water; then 5-30mg of Co is added x Fe y O 4 Performing ultrasonic treatment for 1h; freeze drying to obtain g-C 3 N 4 /Co x Fe y O 4 A composite material.
7. CoFe @ Fe with core-shell structure according to claim 3 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst is characterized by comprising the following steps: in the above step 4, take g-C 3 N 4 /Co x Fe y O 4 Composite material of in CO 2 And H 2 Annealing in the mixed gas, and according to the volume percentage, calculating the H in the mixed gas 2 25-50vol% of CO 2 0-25vol%, ar as equilibrium gas, and 300-600 deg.C; coFe @ Fe with core-shell structure and capable of forming defect-rich carbon support after annealing 3 O 4 An alloy catalyst material.
8. CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 A hydrogenation catalyst characterized by: the core-shell structure of claim 1, wherein CoFe @ Fe 3 O 4 Alloy CO 2 The preparation method of the hydrogenation catalyst.
9. CoFe @ Fe with core-shell structure according to claim 8 3 O 4 Alloy CO 2 A hydrogenation catalyst characterized by: coFe @ Fe with core-shell structure 3 O 4 Uniform size of nanoparticles, and CoFe @ Fe 3 O 4 The nanoparticles are uniformly distributed on the defect-rich carbon support to form a composite structure.
10. CoFe @ Fe with core-shell structure as recited in claim 8 3 O 4 Alloy CO 2 The application of the hydrogenation catalyst is characterized in that: coFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalysts as CO 2 Catalyst material for hydrogenation reaction.
CN202211328306.0A 2022-10-26 2022-10-26 CoFe @ Fe with core-shell structure 3 O 4 Alloy CO 2 Hydrogenation catalyst, preparation method and application thereof Pending CN115646492A (en)

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