CN116408095A - Crystal face adjustable catalyst for carbon dioxide and ethane reaction and preparation method thereof - Google Patents

Crystal face adjustable catalyst for carbon dioxide and ethane reaction and preparation method thereof Download PDF

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CN116408095A
CN116408095A CN202310175030.5A CN202310175030A CN116408095A CN 116408095 A CN116408095 A CN 116408095A CN 202310175030 A CN202310175030 A CN 202310175030A CN 116408095 A CN116408095 A CN 116408095A
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reaction
catalyst
carbon dioxide
ethane
crystal face
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李秀权
杨仲卿
陈杰
何自强
李聪波
王飞
黄崧
蔡琴
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CHONGQING SPECIAL EQUIPMENT INSPECTION AND RESEARCH INSTITUTE
Chongqing University
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Abstract

The invention relates to the technical field of industrial catalysts, and provides a crystal face adjustable catalyst for the reaction of carbon dioxide and ethane and a preparation method thereof, wherein the catalyst comprises a ceria carrier capable of adjusting and exposing a crystal face structure and an active metal component, the active metal component is of a Fe-Ni bi-component structure, the mole ratio of Fe to Ni is (2-5): 1, and the mass of the active metal component is that of the active metal componentThe fraction is 0.5% -5%; the ceria carrier has a rod-like microstructure, and is prepared by exposing low-index crystal planes with crystal planes (111) and (110), and taking Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is dissolved in absolute ethyl alcohol, and then rod-shaped cerium dioxide is added and fully stirred to obtain mixed solution; transferring the mixed solution into a high-pressure reaction kettle for solvothermal reaction; filtering out the solvothermal reaction precipitate, and cleaning; and drying and roasting the solvothermal reaction precipitate to obtain the rod-shaped cerium oxide supported active metal Fe-Ni catalyst. The invention solves the problems that the selectivity of the existing catalyst product for preparing ethylene by oxidizing ethane with carbon dioxide is poor and the catalytic reaction direction is difficult to regulate and control.

Description

Crystal face adjustable catalyst for carbon dioxide and ethane reaction and preparation method thereof
Technical Field
The invention relates to the technical field of industrial catalysts, in particular to a crystal face adjustable catalyst for the reaction of carbon dioxide and ethane and a preparation method thereof.
Background
The carbon-to-carbon peak neutralization energy technology is the leading edge of world technological research and is also a great demand in China. The most direct way to achieve the "two carbon" strategy goal is to reduce the production and emission of carbon dioxide, on the one hand, the direct combustion use of fossil energy can be transitioned to clean and efficient conversion use to reduce the production of carbon dioxide, and on the other hand, carbon dioxide resources of carbon capture and separation can be utilized to reduce carbon emissions. The oriented catalytic high-efficiency conversion of ethane and carbon dioxide is utilized to produce the value-added product ethylene, so that the recycling utilization of greenhouse gas carbon dioxide and the value-added conversion of ethane in gas energy sources such as shale gas can be simultaneously realized, and the method has good economic and social benefits.
The application of carbon dioxide in preparing ethylene by catalytic oxidative dehydrogenation of ethane can properly reduce the reaction temperature, improve the equilibrium yield of olefin and prolong the service life of the catalyst. In addition, ethane and carbon dioxide are all very stable in structure and the research of the activation process of the ethane and the carbon dioxide and the catalytic reaction between the ethane and the carbon dioxide plays a vital role in understanding the catalytic process of the small molecules and enriching the energy and improving the efficient conversion and utilization. The ethane and carbon dioxide catalytic reaction can realize reforming reaction to generate synthesis gas (CO and H) through C-C bond rupture 2 ) Oxidative dehydrogenation to ethylene can also be achieved by cleavage of the C-H bond. The bond energy of the C-C bond in the alkane molecule is lower than that of the C-H bond, so that the cleavage of the C-C bond occurs thermodynamically more easily than the cleavage of the C-H bond. The dry reforming and oxidative dehydrogenation of ethane essentially involves selective cleavage of the C-C/C-H bonds in ethane at different catalytically active sites, respectively, and efficient oxidative dehydrogenation reactions to ethylene can be achieved by precise design of the catalyst active sites. Therefore, the selective fracture of the C-C bond and the C-H bond in the low-carbon alkane is regulated and controlled through the design of the interface structure of the catalyst surface, and the catalyst has important significance for the efficient catalytic conversion and utilization of carbon-based energy.
Disclosure of Invention
In view of the above, the present application aims to provide a crystal face adjustable catalyst for reaction of carbon dioxide and ethane and a preparation method thereof, which solve the problems that the selectivity of the existing catalyst product for preparing ethylene by oxidative dehydrogenation of ethane by carbon dioxide is poor and the catalytic reaction direction is difficult to regulate.
In order to achieve the technical purpose, the technical scheme adopted by the application is as follows:
in a first aspect, the invention discloses a crystal face adjustable catalyst for the reaction of carbon dioxide and ethane, which comprises a ceria carrier capable of adjusting an exposed crystal face structure and an active metal component, wherein the active metal component is of a Fe-Ni bi-component structure, the molar ratio of Fe to Ni is (2-5): 1, and the mass fraction of the active metal component is 0.5% -5%.
Further, the microstructure of the ceria support is a rod-like structure, and the exposed crystal planes are low-index crystal planes of (111) and (110).
In a second aspect, the invention discloses a method for preparing a crystal face adjustable catalyst for the reaction of carbon dioxide and ethane, which comprises the following steps,
s1, use of Ce (NO) 3 ) 3 ·6H 2 O and NaOH to prepare rod-shaped cerium dioxide;
s2, taking Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is dissolved in absolute ethyl alcohol, and then the rod-shaped cerium dioxide prepared in the step S1 is added and fully stirred to obtain a mixed solution;
s3, transferring the mixed solution obtained in the step S2 into a high-pressure reaction kettle for solvothermal reaction;
s4, filtering out a solvothermal reaction precipitate after the solvothermal reaction is finished, and cleaning the solvothermal reaction precipitate;
s5, drying and roasting the solvothermal reaction precipitate to obtain the rod-shaped cerium oxide supported active metal Fe-Ni catalyst.
Further, the preparation method of the rod-shaped cerium oxide in the step S1 comprises the following steps:
s101, taking Ce (NO) 3 ) 3 ·6H 2 O and NaOH are respectively dissolved in deionized water;
s102, slowly dripping a Ce (NO 3) 3 solution into a NaOH solution, and stirring until an emulsion is formed;
s103, transferring the obtained emulsion into a high-pressure reaction kettle for hydrothermal reaction;
s104, after the hydrothermal reaction is finished, centrifugally separating out a hydrothermal reaction precipitate, and then cleaning to be neutral;
s105, drying and roasting the hydrothermal reaction precipitate obtained by the hydrothermal reaction to obtain the rod-shaped cerium oxide.
Further, ce (NO 3 ) 3 ·6H 2 The concentration of the O solution is 0.4mol/L, and the concentration of the prepared NaOH solution is 6.85mol/L.
Further, in the step S103, the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 24 hours.
Further, in the step S105, the drying temperature of the hydrothermal reaction precipitate is 80 ℃ and the drying time is 12 hours; the roasting temperature is 400 ℃, the roasting time is 4 hours, and the temperature rise rate during roasting is 10 ℃/min.
Further, in the step S3, the solvothermal reaction temperature is 120 ℃ and the solvothermal reaction time is 10h.
Further, in the step S5, the drying temperature of the solvothermal reaction precipitate is 80 ℃ and the drying time is 12 hours; the roasting temperature is 400 ℃, the roasting time is 4 hours, and the roasting temperature rise rate is 2 ℃/min.
Further, in the step S104, deionized water and absolute ethanol are alternately used to wash the hydrothermal reaction precipitate to neutrality.
The invention adopting the technical scheme has the following advantages:
1. the catalyst disclosed by the invention adopts transition metals Fe and Ni as main active components, so that the catalyst not only has higher reactivity and product selectivity, but also avoids the use of noble metals, and reduces the manufacturing cost of the catalyst.
2. Rod-shaped CeO formed by the preparation method of the catalyst 2 The (111) and (110) crystal planes are mainly exposed, wherein the formation of oxygen vacancies enhances the activation of structurally stable carbon dioxide molecules, facilitating the progress of the reaction.
3. The active metal Fe-Ni of the invention is oxidized Fe at a specific proportion of the invention 3+ And Ni in a reduced state 0 The density of the active ingredients is higher, the circulation of oxidation-reduction reaction in ethane dehydrogenation reaction is effectively promoted, and the reaction stability is improved.
Drawings
The present application may be further illustrated by the non-limiting examples given in the accompanying drawings. It is to be understood that the following drawings illustrate only certain embodiments of the present application and are therefore not to be considered limiting of its scope, for the person of ordinary skill in the art may derive other relevant drawings from the drawings without inventive effort.
FIG. 1 is a transmission electron microscope photograph of a morphology structure of a rod-shaped structure supported Fe1.5Ni0.5/CeO2-R catalyst prepared by the invention.
FIG. 2 is a graph of experimental test data of the conversion rate of a rod-shaped structure supported Fe1.5Ni0.5/CeO2-R catalyst reactant prepared by the invention.
FIG. 3 is a graph of experimental test data of selectivity of a supported Fe1.5Ni0.5/CeO2-R catalyst product with a rod-like structure.
Detailed Description
The present application will be described in detail below with reference to the drawings and the specific embodiments, and it should be noted that in the drawings or the description of the specification, similar or identical parts use the same reference numerals, and implementations not shown or described in the drawings are in forms known to those of ordinary skill in the art. In the description of the present application, the terms "first," "second," and the like are used merely to distinguish between descriptions and are not to be construed as indicating or implying relative importance.
Example 1,
The present embodiment is a rod-shaped cerium oxide (CeO) 2 -R) preparation: 3.47376g of Ce (NO) 3 ) 3 .6H 2 O (8 mmol) and 38.4g NaOH (0.96 mol) were dissolved in 20mL and 140mL deionized water, respectively. Ce (NO) 3 ) 3 The solution was slowly added dropwise to the NaOH solution with continuous magnetic stirring for 30min to form an emulsion, which was then transferred to a 200mL autoclave and reacted hydrothermally at 100 ℃ for 24h. After the hydrothermal treatment is finished, naturally cooling the high-pressure reaction kettle, centrifugally separating the precipitate, and then cleaning the precipitate to be neutral by alternately using deionized water and absolute ethyl alcohol. Drying the obtained product at 80 ℃ for 12 hours, roasting at 400 ℃ for 4 hours to obtain CeO 2 -R。
EXAMPLE 2,
The present example is a cubic ceria (CeO) 2 -C) preparation: 3.47376g of Ce (NO) 3 ) 3 .6H 2 O (8 mmol) and 38.4g NaOH (0.96 mol) were dissolved in 20mL and 140mL deionized water, respectively. Ce (NO) 3 ) 3 Slowly dripping the solution into NaOH solution, continuously magnetically stirring for 30min to form emulsion, and transferringTo a 200mL autoclave, and reacted hydrothermally at 180℃for 24 hours. After the hydrothermal treatment is finished, naturally cooling the high-pressure reaction kettle, centrifugally separating the precipitate, and cleaning the precipitate to be neutral by adopting deionized water and absolute ethyl alcohol alternately. Drying the obtained product at 80 ℃ for 12 hours, roasting at 400 ℃ for 4 hours to obtain CeO 2 -C。
EXAMPLE 3,
The present example is a flake ceria (CeO) 2 -P) preparation: 5.208g Ce (NO) 3 ) 3 ·6H 2 O and 60mL of deionized water were mixed, then 1.5g of polyvinylpyrrolidone was added with stirring and stirred for an additional 20 minutes. After a clear solution was formed, 12mL of N was slowly added with stirring 2 H 4 ·H 2 O (85%). The resulting solution was then transferred to a 250mL autoclave and reacted hydrothermally at 180 ℃ for 12h. After the hydrothermal treatment is finished, after the autoclave is naturally cooled, centrifugally separating the precipitate, and then cleaning the precipitate to be neutral by adopting deionized water and absolute ethyl alcohol alternately. Drying the obtained product at 80 ℃ for 12 hours, roasting at 400 ℃ for 4 hours to obtain CeO 2 -P。
EXAMPLE 4,
The present example is octahedral cerium oxide (CeO) 2 -O) preparation: will consist of 1.716g Ce (NO 3 ) 3 ·6H 2 A solution of O and 20mL deionized water was combined with another solution of 0.015g Na 3 PO 4 And 140mL of deionized water. After continuously stirring the obtained solution for half an hour, it was transferred into a 250mL autoclave, and subjected to hydrothermal reaction at 170 ℃ for 10 hours. After the hydrothermal treatment is finished, after the autoclave is naturally cooled, centrifugally separating the precipitate, and then cleaning the precipitate to be neutral by adopting deionized water and absolute ethyl alcohol alternately. Drying the obtained product at 80 ℃ for 12 hours, roasting at 400 ℃ for 4 hours to obtain CeO 2 -O。
EXAMPLE 5,
This example is a rod-shaped cerium oxide (CeO) prepared in example 1 by solvothermal method 2 -R) active metal Fe and Ni loading on support: ceO of the morphology obtained in example 1 loaded with active metals Fe and Ni by solvothermal method 2 And (3) on a carrier. Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 25ml of absolute ethanol, and the solution was then stirred well for 30 minutes and transferred to a 50ml autoclave and reacted hydrothermally at 120℃for 10 hours. Subsequently, the filtered precipitate was washed 3 times with distilled water and dried at 80℃for 12 hours. Thereafter, the above precipitate was raised to 400 ℃ at a temperature-raising rate of 2 ℃/min in a temperature-programmed furnace and calcined for 4 hours. The molar ratio of Fe to Ni in the catalyst composition was (2-5): 1, wherein the molar ratio of Fe to Ni in the present example was 3:1, and the mass content of Ni was 0.5%. The catalyst prepared in this example was designated Fe 1.5 Ni 0.5 /CeO 2 -R。
EXAMPLE 6,
This example is a cubic ceria (CeO) prepared in example 2 by solvothermal method 2 -C) active metal Fe and Ni loading on support: ceO of the morphology obtained in example 1 loaded with active metals Fe and Ni by solvothermal method 2 And (3) on a carrier. Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 25ml of absolute ethanol, and the solution was then stirred well for 30 minutes and transferred to a 50ml autoclave and reacted hydrothermally at 120℃for 10 hours. Subsequently, the filtered precipitate was washed 3 times with distilled water and dried at 80℃for 12 hours. Thereafter, the above precipitate was raised to 400 ℃ at a temperature-raising rate of 2 ℃/min in a temperature-programmed furnace and calcined for 4 hours. The molar ratio of Fe to Ni in the catalyst composition was (2-5): 1, wherein the molar ratio of Fe to Ni in the present example was 2:1, and the mass content of Ni was 0.5%. The catalyst prepared in this example was designated Fe 1.5 Ni 0.5 /CeO 2 -C。
EXAMPLE 7,
This example is a flake ceria (CeO) prepared in example 3 by solvothermal method 2 -P) active metal Fe and Ni loading on support: ceO of the morphology obtained in example 1 loaded with active metals Fe and Ni by solvothermal method 2 And (3) on a carrier. Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 25ml of absolute ethanol, and the solution was then stirred well for 30 minutes and transferred to 50ml of high pressureIn the kettle, the reaction is carried out for 10 hours under 120 ℃ in a hydrothermal mode. Subsequently, the filtered precipitate was washed 3 times with distilled water and dried at 80℃for 12 hours. Thereafter, the above precipitate was raised to 400 ℃ at a temperature-raising rate of 2 ℃/min in a temperature-programmed furnace and calcined for 4 hours. The molar ratio of Fe to Ni in the catalyst composition was (2-5): 1, wherein the molar ratio of Fe to Ni in the present example was 4:1, and the mass content of Ni was 0.5%. The catalyst prepared in this example was designated Fe 1.5 Ni 0.5 /CeO 2 -P。
EXAMPLE 8,
This example is octahedral cerium oxide (CeO) prepared in example 4 by solvothermal method 2 -O) active metal Fe and Ni loading on support: ceO of the morphology obtained in example 1 loaded with active metals Fe and Ni by solvothermal method 2 And (3) on a carrier. Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 25ml of absolute ethanol, and the solution was then stirred well for 30 minutes and transferred to a 50ml autoclave and reacted hydrothermally at 120℃for 10 hours. Subsequently, the filtered precipitate was washed 3 times with distilled water and dried at 80℃for 12 hours. Thereafter, the above precipitate was raised to 400 ℃ at a temperature-raising rate of 2 ℃/min in a temperature-programmed furnace and calcined for 4 hours. The molar ratio of Fe to Ni in the catalyst composition was (2-5): 1, wherein the molar ratio of Fe to Ni in the present example was 5:1, and the mass content of Ni was 0.5%. The catalyst prepared in this example was designated Fe 1.5 Ni 0.5 /CeO 2 -O。
The catalysts prepared in examples 5-8 were subjected to an exposed crystal plane test as follows: the surface morphology, configuration, defect structure, vacancy structure, etc. of the catalyst were studied using transmission electron microscopy. The transmission electron microscope is used for measurement under the working acceleration voltage of 200kV, the length of a camera is 520mm, and the electron wavelength is
Figure BDA0004100534870000051
Firstly, a small amount of sample is taken and ground in a mortar, then dispersed in absolute ethyl alcohol, and after ultrasonic oscillation (40 min) and standing and sedimentation (2 h), a small amount of suspension is absorbed and added dropwise into an ultrathin carbon film copper net or molybdenum netAnd (5) naturally airing. And placing the copper mesh carrying the sample into an electron microscope gun, loading the copper mesh into an electron microscope pretreatment chamber for treatment to a certain vacuum degree, testing, and measuring the lattice fringe spacing of the sample under the high-resolution condition. Rod-shaped structure supported Fe 1.5 Ni 0.5 /CeO 2 The morphology structure transmission electron microscope photograph of the-R catalyst is shown in figure 1.
The catalysts prepared in examples 5 to 8 were then subjected to an effect test, in particular: the catalytic reaction experiments were all carried out in a glass tube reactor (inner diameter 4.5mm, outer diameter 6.5 mm) under normal pressure. The total gas flow in the catalytic reaction experiment is 30ml/min, wherein the ratio of ethane, carbon dioxide and nitrogen is 1:1:1, and the ratio is 10, 10 and 10ml/min respectively. In the experiment, 200mg of catalyst was taken, uniformly mixed with 600mg of quartz sand (30-40 mesh), and then filled into a quartz tube reactor. The catalysts tested by the experiments were subjected to a reducing atmosphere (10% H) at a flow rate of 20ml/min 2 ) The catalyst was then reduced in situ by heating to 550℃in a heating furnace at a heating rate of 10℃per minute for 1 hour. After the reduction of the catalyst is finished, waiting for the temperature of the bed to be reduced to below 200 ℃, and then switching the gas path to be the reaction gas. The catalyst was heated to 650 ℃ in a reaction atmosphere by a heating furnace at a heating rate of 10 ℃/min, and then maintained for 1 hour to reach a quasi-steady state, after which the tail gas composition detection was started. CeO regulated into rod shape through morphology structure 2 The supported catalyst has higher reaction conversion rate and high value product C 2 H 4 The selectivity of (2) is shown in the following table.
TABLE 1 reactivity of catalysts
Figure BDA0004100534870000061
The catalysts prepared in examples 5 to 8 were further subjected to stability tests as follows: and the reaction conditions are the same as those in the effect test, and the tail gas is continuously detected for 8 hours after the reaction temperature is switched to the reactant gas. The catalytic reaction of ethane with carbon dioxide by the different catalysts varies drastically during the initial phase (IS, 0-100 min), and after reaching a quasi-steady state (PS,>100 min) stateThe post reaction becomes smooth. Fe (Fe) 1.5 Ni 0.5 /CeO 2 R catalyst reactant conversion stability is shown in FIG. 2 and product selectivity is shown in FIG. 3. Can obtain rod-like Fe under long-term reaction 1.5 Ni 0.5 /CeO 2 The R catalyst has higher reaction performance and shows better reaction stability.
The foregoing is merely exemplary embodiments of the present application and is not intended to limit the scope of the present application, and various modifications and variations may be suggested to one skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (10)

1. A crystal face adjustable catalyst for the reaction of carbon dioxide with ethane, characterized by: the catalyst comprises a ceria carrier with an adjustable exposed crystal face structure and an active metal component, wherein the active metal component is of a Fe-Ni dual-component structure, the molar ratio of Fe to Ni is (2-5): 1, and the mass fraction of the active metal component is 0.5% -5%.
2. A crystal face tunable catalyst for the reaction of carbon dioxide with ethane according to claim 1, wherein: the microstructure of the ceria support is a rod-shaped structure, and the exposed crystal faces are low-index crystal faces of (111) and (110).
3. A preparation method of a crystal face adjustable catalyst for carbon dioxide and ethane reaction is characterized by comprising the following steps of: comprises the steps of,
s1, use of Ce (NO) 3 ) 3 ·6H 2 O and NaOH to prepare rod-shaped cerium dioxide;
s2, taking Fe (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is dissolved in absolute ethyl alcohol, and then the rod-shaped cerium dioxide prepared in the step S1 is added and fully stirred to obtain a mixed solution;
s3, transferring the mixed solution obtained in the step S2 into a high-pressure reaction kettle for solvothermal reaction;
s4, filtering out a solvothermal reaction precipitate after the solvothermal reaction is finished, and cleaning the solvothermal reaction precipitate;
s5, drying and roasting the solvothermal reaction precipitate to obtain the rod-shaped cerium oxide supported active metal Fe-Ni catalyst.
4. A process for preparing a crystal face tunable catalyst for carbon dioxide reaction with ethane according to claim 3, wherein: the preparation method of the rod-shaped cerium oxide in the step S1 comprises the following steps:
s101, taking Ce (NO) 3 ) 3 ·6H 2 O and NaOH are respectively dissolved in deionized water;
s102, slowly dripping a Ce (NO 3) 3 solution into a NaOH solution, and stirring until an emulsion is formed;
s103, transferring the obtained emulsion into a high-pressure reaction kettle for hydrothermal reaction;
s104, after the hydrothermal reaction is finished, centrifugally separating out a hydrothermal reaction precipitate, and then cleaning to be neutral;
s105, drying and roasting the hydrothermal reaction precipitate obtained by the hydrothermal reaction to obtain the rod-shaped cerium oxide.
5. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 4, wherein: the Ce (NO) formulated in the step S101 3 ) 3 ·6H 2 The concentration of the O solution is 0.4mol/L, and the concentration of the prepared NaOH solution is 6.85mol/L.
6. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 5, wherein: in the step S103, the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 24 hours.
7. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 6, wherein: in the step S105, the drying temperature of the hydrothermal reaction precipitate is 80 ℃ and the drying time is 12 hours; the roasting temperature is 400 ℃, the roasting time is 4 hours, and the temperature rise rate during roasting is 10 ℃/min.
8. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 7, wherein: in the step S3, the solvothermal reaction temperature is 120 ℃, and the solvothermal reaction time is 10 hours.
9. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 8, wherein: in the step S5, the drying temperature of the solvothermal reaction precipitate is 80 ℃ and the drying time is 12 hours; the roasting temperature is 400 ℃, the roasting time is 4 hours, and the roasting temperature rise rate is 2 ℃/min.
10. The method for preparing a crystal face adjustable catalyst for carbon dioxide and ethane reaction according to claim 9, wherein: in the step S104, deionized water and absolute ethyl alcohol are alternately used to wash the hydrothermal reaction precipitate to neutrality.
CN202310175030.5A 2023-02-28 2023-02-28 Crystal face adjustable catalyst for carbon dioxide and ethane reaction and preparation method thereof Pending CN116408095A (en)

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