CN115254100A - For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation - Google Patents

For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation Download PDF

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CN115254100A
CN115254100A CN202211039495.XA CN202211039495A CN115254100A CN 115254100 A CN115254100 A CN 115254100A CN 202211039495 A CN202211039495 A CN 202211039495A CN 115254100 A CN115254100 A CN 115254100A
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catalyst
salt
hydrogenation
carrier
metal oxide
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刘小浩
郑珂
李玉峰
刘冰
胥月兵
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Jiangnan University
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Abstract

The invention discloses a method for preparing CO 2 Preparation and application of a metal oxide doped monatomic catalyst for preparing ethanol by hydrogenation belong to the field of carbon dioxide conversion application. The catalyst consists of an active component and a doped carrier, wherein the active component comprises one or more of Rh, pd, ir, fe, co, ni and Cu; the doped carrier comprises CeO 2 、TiO 2 、In 2 O 3 、Al 2 O 3 、ZnO、SiO 2 、MnO 2 And Cr 2 O 3 Two or more of them. The Rh monatomic catalyst constructed by intercalating monatomic Rh into a doped carrier of the catalyst of the present invention exhibits excellent CO 2 Hydrogenation performance, ethanol selectivity is more than 99 percent, and stability is higher. The invention realizes the regulation and control of the surface property of the carrier by doping the carrier, thereby improving the dispersibility and structural stability of the loaded active metal and improving CO 2 The catalytic performance of hydrogenation ethanol preparation.

Description

For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation
Technical Field
The invention relates to a method for CO 2 Preparation and application of a metal oxide doped monatomic catalyst for preparing ethanol by hydrogenation belong to the field of carbon dioxide conversion application.
Background
The heavy use of fossil fuels has led to the concentration of carbon dioxide in the atmosphere reaching unprecedented levels, which has serious consequences for the global environment and human development that are not negligible. At the same time, CO 2 Is also a nontoxic, cheap, rich and renewable C1 resource, so that CO is used as a raw material 2 The conversion into high value-added chemicals has important practical significance. Ethanol is an important basic chemical raw material, which is widely used as a disinfectant, a reaction solvent, and a gasoline additive. The direct conversion of carbon dioxide to ethanol is an ideal process for eliminating greenhouse gases and producing valuable products. However, this process is hampered by low activity, which is due to CO 2 High thermodynamic stability and chemical inertness of, and by-products (e.g. CH) 4 CO and CH 3 OH, etc.). Therefore, the development of highly active and highly selective catalysts for ethanol production remainsIs a significant challenge.
Reported CO 2 The catalytic system for preparing the ethanol by hydrogenation mainly comprises a noble metal base, a Co base, a Cu base, a Fe base and a multi-element composite catalyst system. Among them, the noble metal-based catalyst shows a high selectivity to ethanol. However, since the noble metal is expensive, it is imperative to maximize the utilization efficiency of the noble metal for practical use. Monatomic catalysts, which refer to isolated metal atoms supported on the surface of a carrier as active sites, are receiving wide attention due to their unique catalytic behavior and 100% efficiency. However, the limited active metal component loading in the monatomic catalyst determines that the catalyst activity is low, and the practical application is greatly limited. At the same time, due to the lack of proper metal-support interaction, the monoatomic active sites are prone to migration and aggregation, resulting in poor catalytic stability.
Therefore, the development of a new monatomic catalyst for ethanol production by carbon dioxide hydrogenation with high activity, high selectivity and excellent stability remains a difficult challenge.
Disclosure of Invention
In order to solve the problems, the invention adopts a doping strategy to regulate and control the quantity and the property of oxygen vacancies on the surface of the carrier, so that the carrier can anchor metal atoms more easily in a high-temperature environment, and a monatomic catalyst with high dispersion and high stability is obtained. The catalyst is in CO 2 In the process of preparing ethanol by hydrogenation, CO can be obtained 2 High-efficiency catalytic conversion to ethanol product with high added value, and effective reduction of by-products such as CO and CH 4 And CH 3 OH is formed and has higher stability.
It is a first object of the present invention to provide a catalyst for catalyzing CO 2 The preparation method of the metal oxide doped monatomic catalyst for preparing ethanol by hydrogenation comprises the following steps:
(1) Dissolving a carrier precursor in water, adding a precipitator, uniformly mixing, and carrying out hydrothermal reaction; wherein, the carrier precursor is any two or more than two of water-soluble cerium salt, zirconium salt, indium salt, zinc salt, chromium salt, manganese salt, aluminum salt and titanate; after the reaction is finished, filtering, collecting solids, drying, and roasting at 300-800 ℃ to obtain a metal oxide doped carrier;
(2) Dispersing a metal oxide doped carrier in an organic solvent to obtain a suspension, adding an active metal precursor into the suspension, stirring for 5-20 h, removing the organic solvent to obtain a solid, and roasting to obtain a metal oxide doped monatomic catalyst; the active metal is selected from one or more of Rh, pd, ir, fe, co, ni and Cu.
In one embodiment of the present invention, the concentration of the metal in the support precursor in step (1) relative to water is 0.2 to 1.0mol/L. Specifically, 0.5mol/L can be selected.
In one embodiment of the present invention, the carrier precursor in step (1) is one or more of water-soluble nitrate, acetate, sulfate and acetylacetonate.
In one embodiment of the invention, the carrier precursor in step (1) comprises a main component and a doping component, each of which is independently selected from one or more of water-soluble cerium salt, zirconium salt, indium salt, zinc salt, chromium salt, manganese salt, aluminum salt and titanate, and the main component and the doping component are different; the molar ratio of the metal in the main component to the metal in the doping component is 1.
In one embodiment of the invention, in the step (1), the main component is preferably one or more of water-soluble cerium salt, indium salt, zinc salt, aluminum salt and titanate, and the doping component is preferably one or more of zirconium salt, chromium salt, manganese salt and titanate; and the main component and the doped component are different from titanate.
In one embodiment of the present invention, the titanate may be specifically tetrabutyl titanate.
In one embodiment of the present invention, the precipitating agent in step (1) is one or more of urea, sodium salt, potassium salt and ammonia water.
In one embodiment of the invention, the concentration of the precipitant in step (1) relative to water is 0.8 to 1.5mol/L.
In one embodiment of the invention, the precipitant is added in step (1) and stirred vigorously at 30-100 ℃ to achieve uniform mixing.
In one embodiment of the present invention, the conditions of the hydrothermal reaction in step (1) are: heating the mixture in a high-pressure kettle to 50-120 ℃ for reaction for 5-100 h, and then heating the mixture to 120-200 ℃ for continuous reaction for 1-20 h.
In one embodiment of the present invention, the calcination time in step (1) is 1 to 10 hours.
In one embodiment of the present invention, the organic solvent in step (2) is acetone.
In one embodiment of the present invention, the concentration of the metal oxide-doped carrier in the suspension in the step (2) is 0.02 to 0.1g/mL; specifically, 0.05g/mL may be used.
In one embodiment of the present invention, the active metal precursor in step (2) is one or more of nitrate, acetate, sulfate and acetylacetonate of the active metal.
In one embodiment of the present invention, the amount of the active metal in the active metal precursor in step (2) is 0.01mmol/g relative to the support.
In one embodiment of the present invention, the temperature of the calcination in the step (2) is 800 ℃ and the time is 10 hours.
The invention provides a preparation method of the catalyst, which comprises the following steps:
(1) Dissolving a corresponding precursor of the carrier in water, adding a precipitator, violently stirring at 30-100 ℃, transferring to a stainless steel autoclave, carrying out hydrothermal treatment at 50-120 ℃ for 5-100 h in an oven, and then heating to 120-200 ℃ for 1-20 h. Finally, filtering and washing the hydrothermal product, drying at 60-150 ℃ overnight, and roasting in a muffle furnace at 300-800 ℃ for 1-10 h to obtain a carrier;
(2) Dispersing a carrier in an acetone solvent, carrying out ultrasonic treatment for 1-10 h to obtain a well-dispersed suspension, adding a precursor corresponding to an active component into the suspension, continuously stirring for 5-20 h, carrying out rotary evaporation to obtain a solid, and roasting at 800 ℃ for 10h to obtain the catalyst.
The invention provides a catalyst for catalyzing CO based on the preparation method 2 Metal oxide doping type for preparing ethanol by hydrogenationA monatomic catalyst.
In one embodiment of the invention, the active component in the catalyst is highly dispersed on the carrier at atomic level, and the active component comprises one or more of Rh, pd, ir, fe, co, ni and Cu; the carrier comprising CeO 2 、TiO 2 、In 2 O 3 、Al 2 O 3 、ZnO、SiO 2 、MnO 2 、Cr 2 O 3 And ZrO 2 Two or more of them.
In one embodiment of the invention, the content of the active component in the catalyst accounts for 0.01-10% of the total mass of the catalyst; the carrier accounts for 90-99.99% of the total mass of the catalyst.
In one embodiment of the invention, the active ingredient is highly dispersed on the carrier at the atomic level.
The invention also provides CO 2 The method for preparing the ethanol by hydrogenation takes the catalyst as a hydrogenation catalyst.
In one embodiment of the invention, the process is carried out in CO 2 CO is introduced into the catalyst for preparing the ethanol by hydrogenation 2 /H 2 Synthesis gas, CO in batch reactor, fixed bed or slurry bed 2 Hydrogenation reaction for preparing ethanol.
In one embodiment of the invention, the catalyst is subjected to activation pretreatment before use, wherein the pretreatment atmosphere is hydrogen or carbon monoxide, the pressure is 0.1-2 MPa, the temperature is 300-600 ℃, and the time is 1-10 h.
In one embodiment of the invention, the CO is 2 The reaction conditions for preparing the ethanol by hydrogenation are as follows: CO 2 2 :H 2 1-8, the reaction temperature is 100-350 ℃, and the reaction pressure is 1-10 MPa.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention introduces a metal oxide doping concept for regulating and controlling the quantity and the property of oxygen vacancies on the surface of the catalyst, and the surface of the catalyst carrier obtained after doping exposes more oxygen vacancies, can effectively anchor active component atoms and obtains a high degreeA dispersed monatomic catalyst. The Rh monatomic catalyst constructed by intercalating monatomic Rh into a doped carrier of the catalyst of the present invention exhibits excellent CO 2 Hydrogenation performance, ethanol selectivity is more than 99 percent, and stability is higher. The invention realizes the regulation and control of the surface property of the carrier by doping the carrier, thereby improving the dispersibility and the structural stability of the loaded active metal and improving CO 2 The catalytic performance of ethanol preparation by hydrogenation.
(2) The doping strategy provided by the invention can effectively regulate and control the interaction between the active component and the carrier, so that the active component is difficult to agglomerate and sinter, and higher stability is shown.
Drawings
FIG. 1 is a schematic diagram of the catalyst structure (Ti-doped CeO) 2 Rh monatomic catalyst supported on a carrier) with monatomic active components inside the dotted circle.
Detailed Description
While the present invention will be described in conjunction with specific examples for the purpose of illustrating the invention more clearly, it is to be understood that the particulars shown below are by way of illustration and not of limitation, and are not to be taken by way of limitation, the scope of the present invention being limited thereby.
The catalyst performance evaluation was carried out in a batch tank reactor. The specific catalytic performance evaluation method is as follows: and (3) carrying out reduction activation treatment on the catalyst. Wherein the catalyst activation pretreatment conditions are as follows: the pretreatment atmosphere is high-purity hydrogen, the pressure is 0.1MPa, the temperature is 300 ℃, and the time is 1h. After the reduction is finished, CO is added 2 :H 2 The feed gas of = 1. The mass of the catalyst is 30mg, the solvent is water, the volume of the solvent is 20mL, the rotating speed is 400rpm, and the reaction time is 5h. And the gas product enters a chromatograph for on-line analysis, and the liquid product is analyzed through a nuclear magnetic resonance spectrogram.
CO 2 Conversion = (CO before reaction) 2 Mole-number-of-reacted CO 2 mole)/CO before reaction 2 Mole number × 100%;
product selectivity = product moles x product moleculesCarbon number/(CO before reaction) 2 Mole-number-of-reacted CO 2 Mole) × 100%.
CO 2 The catalyst system for preparing the ethanol by hydrogenation and the preparation method thereof are as follows:
example 1
Firstly, dissolving cerium nitrate and tetrabutyl titanate with a molar ratio of cerium to titanium of 0.3 in 80mL of deionized water to form a cerium-titanium mixed solution, wherein the total molar concentration of cerium and titanium in the cerium-titanium mixed solution is 0.5mol/L; then 5.586g of urea was added to the cerium-titanium mixed solution, mixed and stirred vigorously at 50 ℃, hydrothermal at 80 ℃ for 48h, and then heated to 120 ℃ for 5h. Finally, the hydrothermal product was filtered and washed with ethanol, dried at 120 ℃ overnight, and calcined in a muffle furnace at 400 ℃ for 4h to give Ti doped CeO 2 Supported Rh monatomic catalyst, designated CeTiO x A carrier;
second, 1g of CeTiO x Dispersing the carrier in 20mL of acetone solvent, carrying out ultrasonic treatment for 2h, then adding 0.0039g of rhodium acetylacetonate, continuing stirring for 10h, carrying out rotary evaporation to obtain a solid, and roasting at 800 ℃ for 10h to obtain Rh/CeTiO x A catalyst. The Rh element content in the catalyst was 0.1wt%.
Example 2
The carrier precursor in the first step of example 1 is changed into indium nitrate and zirconium nitrate (the molar ratio of indium to zirconium is 0.3 x A catalyst.
Example 3
The carrier precursor in the first step of the embodiment 1 is changed into zinc nitrate and zirconium nitrate (the molar ratio of zinc to zirconium is 0.3 x A catalyst.
Example 4
The tetrabutyl titanate in the first step of example 1 is changed into chromium nitrate (the molar ratio of cerium to chromium is 0.3 x A catalyst.
Example 5
The carrier precursor of the first step of example 1 was changed to titanium nitrate and manganese nitrate (molar ratio of titanium to manganese was 0.3)1), the rest steps and operations are unchanged, and Rh/TiMnO is obtained x A catalyst.
Example 6
The cerium nitrate in the first step of example 1 was changed to aluminum nitrate (aluminum/titanium molar ratio 0.3 x A catalyst.
Example 7
The tetrabutyl titanate in the first step of example 1 is changed into manganese nitrate (the molar ratio of cerium to manganese is 0.3 x A catalyst.
Example 8
The rhodium acetylacetonate obtained in the second step of example 1 was replaced by palladium acetate in equimolar amount, and the remaining steps and operations were not changed to obtain Pd/CeTiO x A catalyst.
Example 9
The rhodium acetylacetonate obtained in the second step of example 1 was changed to nickel nitrate in equimolar amount, and the remaining steps and operations were not changed to obtain Ni/CeTiO x A catalyst.
Example 10
The rhodium acetylacetonate obtained in the second step of example 1 was changed to iridium acetate in equimolar amount, and the remaining steps and operations were not changed to obtain Ir/CeTiO x A catalyst.
Example 11
The rhodium acetylacetonate obtained in the second step of example 1 was changed to cobalt nitrate in equimolar amount, and the remaining steps and operations were not changed to obtain Co/CeTiO x A catalyst.
Example 12
The rhodium acetylacetonate obtained in the second step of example 1 was changed to copper nitrate in an equimolar amount, and the remaining steps and operations were not changed to obtain Cu/CeTiO x A catalyst.
CO 2 The application of the catalyst for preparing the ethanol by hydrogenation comprises the following steps:
the catalyst is placed in a batch reactor, the mass of the catalyst is 30mg, the volume of the solvent is 20mL, the rotating speed is 400rpm, and the reaction is carried out for 5h under the reaction conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 1. The reacted catalyst was recovered and labeled run N (N is the number of cycles) for the next cycle test. The results of the catalytic performance of the catalyst are shown in table 1.
Example 13
Rh/CeTiO is added x The catalyst is placed in a batch reactor, the reaction temperature is changed to 100 ℃, and other parameters are unchanged. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 1.
Example 14
Rh/CeTiO is added x The catalyst is placed in a batch reactor, the reaction pressure is changed to 1MPa, and the other parameters are unchanged. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 1.
Example 15
Rh/CeTiO is added x The catalyst was placed in a batch still reactor, the water volume was changed to 5mL, and the remaining parameters were unchanged. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 1.
TABLE 1 catalytic Properties of different catalysts
Figure BDA0003819531480000061
Figure BDA0003819531480000071
As can be seen from the results in Table 1, the catalyst prepared by the catalyst preparation method of the present invention is used in CO 2 Shows high ethanol selectivity in ethanol preparation by hydrogenation>99%) and after five times of cycle tests, the catalyst can still maintain better catalytic performance and shows good catalytic stability.
Comparative example 1
Cerium nitrate and urea were dissolved in water (total molar concentration of metals in water was controlled to be the same), and CeO was obtained by the same procedure as in example 1 2 A carrier; other catalyst preparation procedures were the same as in example 1 to obtain Rh/CeO 2 Catalyst and CO in a batch kettle reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. Rotating shaftThe results of conversion and selectivity or distribution of the individual products are shown in Table 2.
Comparative example 2
Tetrabutyl titanate and urea are dissolved in water (the total molar concentration of metal in water is controlled to be the same), the rest steps are the same as the example 1, and TiO is obtained 2 A carrier; the other catalyst preparation procedure was the same as in example 1 to obtain Rh/TiO 2 Catalyst and CO in a batch kettle reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 2.
Comparative example 3
Indium nitrate and urea were dissolved In water (total molar concentration of metals In water was controlled to be the same), and In was obtained by the same procedure as In example 1 2 O 3 A carrier; the other catalyst preparation procedure was the same as In example 1 to obtain Rh/In 2 O 3 Catalyst and CO in a batch kettle reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 2.
Comparative example 4
Zirconium nitrate and urea were dissolved in water (the total molar concentration of metals in water was controlled to be the same), and the procedure was the same as in example 1 to obtain ZrO 2 A carrier; the other catalyst preparation procedure was the same as in example 1 to obtain Rh/ZrO 2 Catalyst and CO in a batch kettle reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 2.
Comparative example 5
Dissolving zinc nitrate and urea in water (controlling the total molar concentration of the metals in the water to be the same), and performing the rest steps in the same way as in the example 1 to obtain a ZnO carrier; the other catalyst preparation steps were the same as in example 1 to obtain Rh/ZnO catalyst, and CO was carried out in a batch reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 2.
TABLE 2 different catalysts vs. CO 2 Catalytic performance of hydrogenation
Figure BDA0003819531480000081
As can be seen from the results in Table 2, rh catalyst CO supported on a single carrier 2 The conversion and the ethanol selectivity were both low, and the performance of the catalyst after five cycles was significantly reduced, showing poor stability.
Comparative example 6
The non-doped catalyst was prepared using the cerium nitrate, tetrabutyl titanate and rhodium acetylacetonate raw materials of example 1:
(1) 3g of CeO 2 The carrier is 30% of 2 Raising the temperature to 340 ℃ at the speed of 2 ℃/min under the atmosphere of CO, keeping the temperature for 2h, and controlling the space velocity to be 6000mL/g/h;
(2) 3g of treated CeO 2 Dispersing the carrier in a mixed solvent containing 500mL of deionized water and 100mL of glycol solution, and carrying out ultrasonic treatment for 3h; an aqueous rhodium acetylacetonate solution was added under ultrasound and the suspension was stirred for a further 10h. Centrifuging to obtain solid, washing with deionized water and ethanol to make neutral, drying, and calcining at 200 deg.C for 1 hr.
(3) And (3) dispersing the solid obtained in the step (2) in 50mL of deionized water, performing ultrasonic dispersion for 1h, adding a precursor tetrabutyl titanate (the molar ratio of cerium to titanium is 0.3. Then slowly rotating, evaporating and drying the solid-liquid mixture, and finally roasting at 350 ℃ for 3h to obtain the catalyst Rh-CeO 2 -TiO 2 . The Rh element content in the catalyst was 0.1wt%.
And CO is carried out in a batch kettle reactor 2 The hydrogenation performance was evaluated under the conditions of 250 ℃ and 3MPa. The conversion and the results of the selectivity or distribution of the individual products are shown in Table 3.
TABLE 3 Rh-CeO 2 -TiO 2 Catalyst pair CO 2 Catalytic performance of hydrogenation
Figure BDA0003819531480000091
As can be seen from the results in table 3, the doped supported monatomic catalyst prepared according to the present invention has superior catalytic activity and stability compared to the prior similar schemes.
The above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the present invention. Various changes or modifications may be effected by one skilled in the art in light of the foregoing description. It is not exhaustive here for all embodiments. Therefore, the protection scope of the present invention should be subject to the definition of the claims.

Claims (10)

1. For catalyzing CO 2 The preparation method of the metal oxide doped monatomic catalyst for preparing ethanol by hydrogenation is characterized by comprising the following steps:
(1) Dissolving a carrier precursor in water, adding a precipitator, uniformly mixing, and carrying out hydrothermal reaction; wherein, the carrier precursor is any two or more than two of water-soluble cerium salt, zirconium salt, indium salt, zinc salt, chromium salt, manganese salt, aluminum salt and titanate; after the reaction is finished, filtering, collecting solids, drying, and roasting at 300-800 ℃ to obtain a metal oxide doped carrier;
(2) Dispersing a metal oxide doped carrier in an organic solvent to obtain a suspension, adding an active metal precursor into the suspension, stirring for 5-20 h, removing the organic solvent to obtain a solid, and roasting to obtain a metal oxide doped monatomic catalyst; the active metal is selected from one or more of Rh, pd, ir, fe, co, ni and Cu.
2. The method of claim 1, wherein the concentration of metal in the support precursor of step (1) relative to water is from 0.2 to 1.0mol/L.
3. The method according to claim 1, wherein the carrier precursor in step (1) is one or more of water-soluble nitrate, acetate, sulfate and acetylacetonate.
4. The method according to claim 1, wherein the carrier precursor in step (1) comprises a main component and a doping component, each of which is independently selected from one or more of water-soluble cerium salt, zirconium salt, indium salt, zinc salt, chromium salt, manganese salt, aluminum salt and titanate, and the main component and the doping component are different; the molar ratio of the metal in the main component to the metal in the doping component is 1.
5. The method according to claim 1, wherein the precipitating agent in step (1) is one or more of urea, sodium salt, potassium salt and ammonia water.
6. The method according to claim 1, wherein the conditions of the hydrothermal reaction in step (1) are: heating the mixture in a high-pressure kettle to 50-120 ℃ for reaction for 5-100 h, and then heating the mixture to 120-200 ℃ for continuous reaction for 1-20 h.
7. The process according to any one of claims 1 to 6, wherein the concentration of the metal oxide-doped support in the suspension in step (2) is from 0.02 to 0.1g/mL.
8. A catalyst for catalyzing CO prepared by the process of any one of claims 1 to 7 2 A metal oxide doped monatomic catalyst for preparing ethanol by hydrogenation.
9. CO (carbon monoxide) 2 A process for producing ethanol by hydrogenation, wherein the metal oxide-doped monatomic catalyst according to claim 8 is used as a hydrogenation catalyst.
10. The method of claim 9, wherein the method comprises introducing CO into the metal oxide-doped monatomic catalyst of claim 8 2 /H 2 Synthesis gas, CO in batch reactor, fixed bed or slurry bed 2 Hydrogenation reaction for preparing ethanol.
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CN115888683A (en) * 2022-11-15 2023-04-04 北京化工大学 Zinc monoatomic catalyst, preparation method thereof and application thereof in catalytic preparation of N-formyl compound
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CN116273032A (en) * 2023-03-28 2023-06-23 中国科学院山西煤炭化学研究所 Cr-K modified copper-iron composite oxide, preparation method and application thereof, and method for preparing low-carbon alcohol by carbon dioxide hydrogenation
CN116474812A (en) * 2023-04-25 2023-07-25 天津大学 Preparation method of catalyst for catalyzing VOCs oxidation

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