CN112495417A - Iron monatomic catalyst and preparation method and application thereof - Google Patents
Iron monatomic catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an iron monatomic catalyst and a preparation method and application thereof, and the preparation method comprises the following steps: (1) dispersing ferric salt and zinc nitrate in water to prepare a first solution, and dispersing 2-methylimidazole and amine in water to prepare a second solution; mixing the first solution and the second solution, and reacting to generate a solid intermediate; (2) calcining the obtained intermediate in a protective atmosphere to prepare an iron-nitrogen co-doped porous carbon material type iron monatomic catalyst, wherein the iron monatomic is uniformly dispersed and firmly combined; compared with other catalysts for the reduction reaction of the paranitroarene, the iron monatomic catalyst prepared by the method has better activity, more excellent selectivity and stability and high catalytic efficiency; meanwhile, the method for preparing the iron monatomic catalyst has the advantages of simple process, cheap and easily-obtained raw materials, mild and environment-friendly conditions and easy large-scale production.
Description
Technical Field
The invention belongs to the field of preparation of monatomic catalysts, and particularly relates to an iron monatomic catalyst, a preparation method thereof and application thereof in catalyzing reduction of nitroaromatic.
Background
Arylamine compounds are a very important class of chemical intermediates, which have wide applications in the synthesis of medicines, pesticides, dyes, additives, surfactants, textile auxiliaries, chelating agents and polymers. Most aromatic amines are made by reduction of the corresponding nitroarenes. Compared with the traditional iron powder reduction method, the method has the advantages of wide application range, simple process and the like, but the process can generate a large amount of waste water and waste residues, so that the post-treatment is difficult, and the product quality is low. At the same time, the alkali sulfide method is adopted, but the efficiency is low, the method is generally used for preparing arylamine by reducing special raw materials, and harmful gases are released in the reaction process, so that the operation and the environment are not favorable.
At present, the catalytic reduction of nitroarenes to aniline is undoubtedly the most effective method for the selective reduction of aniline today (Applied Catalysis B: Environmental 2018,227,386). The catalytic reduction of nitroaromatic to prepare aniline mainly includes the following three methods, namely catalytic hydrogenation reduction method, hydrazine hydrate reduction method and carbon monoxide reduction method. The hydrazine hydrate reduction method has the advantages of small equipment investment, mild reaction conditions, high reduction yield, capability of carrying out partial reduction, no generation of waste gas and waste residue and the like (Chemistry, an Asian Journal 2017,12 and 785), and is particularly suitable for the production of short-route aromatic amine compounds in small batches. The common catalysts used in hydrazine hydrate reduction process are noble metal catalysts such as Pd, Pt, Au, etc., and in recent years, researchers have developed various cheap metal catalysts (Chemical Communications 2016,52, 4199; Chemical Communications2011,47,10972; Angewandte Chemistry 2012,51, 10190; Green Chemistry 2016,18,2435) successively for the process. However, these catalysts have more or less significant problems, such as low catalytic efficiency, poor reaction selectivity, harsh reaction conditions, poor substrate tolerance, etc.
The monatomic catalyst presents activity, selectivity and stability which are obviously different from those of the conventional nano-catalyst due to the special structure (Chemical Reviews 202010.1021/acs. chemrev.9b00818), but at present, no monatomic catalyst aiming at reducing the nitroarene exists, and the iron monatomic prepared by some existing methods has undesirable effect on reducing the nitroarene and is difficult to realize high-efficiency catalytic reduction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an iron monatomic catalyst suitable for reducing nitroaromatic, the iron monatomic catalyst prepared by the method has excellent catalytic performance for the reduction reaction of the nitroaromatic, the reaction condition is mild, and the selectivity and the substrate tolerance are good; in addition, the preparation method of the catalyst is simple and environment-friendly, and the raw materials are cheap and easy to obtain, so that the catalyst is easy for large-scale production.
The invention also provides an iron monatomic catalyst prepared by the method, which is in the form of an iron-nitrogen co-doped porous carbon material.
The invention also provides an application of the iron monatomic catalyst prepared by the method in catalytic reduction of nitroaromatic.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) dispersing ferric salt and zinc nitrate in water to prepare a first solution, and dispersing 2-methylimidazole and amine in water to prepare a second solution;
mixing the prepared first solution and the second solution, and reacting to generate a solid intermediate;
(2) and (2) calcining the intermediate obtained in the step (1) in a protective atmosphere to prepare the iron monatomic catalyst in the form of an iron-nitrogen co-doped porous carbon material.
In the context of the present invention, the iron monatomic catalyst is denoted as FeSA@ NC-XA, where Fe represents an iron atom, SA represents a single atom, NC represents a nitrogen-doped carbon material, A represents an amine, and X represents a Zn/Fe molar ratio.
According to the invention, in the step (1), the amine is one or a combination of more of aniline, oleylamine, n-butylamine and benzylamine, and compared with other amine compounds, the specific amine has better iron monoatomic ability to be anchored, can be coated on the surface of ZIFs, and inhibits the growth of ZIFs particles, so that ZIFs with smaller particle size are formed, and the method is favorable for inhibiting the agglomeration of iron atoms in the high-temperature pyrolysis process to obtain the uniformly dispersed iron monoatomic catalyst.
According to some preferred and specific aspects of the present invention, in step (1), the iron salt is a combination of one or more selected from the group consisting of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous phosphate.
According to some preferred and specific aspects of the present invention, in step (1), the zinc nitrate is zinc nitrate hexahydrate.
According to some preferred aspects of the invention, in the step (1), the feeding molar ratio of the iron salt, the zinc nitrate, the amine and the 2-methylimidazole is 1: 10-30: 40-120. More preferably, in the step (1), the feeding molar ratio of the iron salt, the zinc nitrate, the amine and the 2-methylimidazole is 1: 15-25: 50-100.
According to the invention, in the step (1), the first solution is added into the second solution under the condition of stirring, stirred, mixed and reacted.
According to some preferred aspects of the invention, in step (1), the first solution is added to the second solution under stirring, the suspension is stirred for a further period of time, and after the reaction is finished, the solid obtained is separated by centrifugation, washed with water several times and dried at 55-65 ℃ for 10-14 h.
According to some preferred aspects of the present invention, in the step (1), the reaction is performed at a temperature of 25 to 50 ℃.
According to some preferred aspects of the present invention, in the step (2), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
According to some preferred aspects of the present invention, in the step (2), the calcination is performed at 800 to 1000 ℃.
According to some preferable aspects of the invention, in the step (2), during the calcining, the temperature rise rate is 5-15 ℃/min, and the calcining time is 2-4 h.
According to some specific aspects of the invention, the calcining is performed in a tube furnace.
The invention provides another technical scheme that: the iron monatomic catalyst prepared by the preparation method is in the form of an iron-nitrogen co-doped porous carbon material.
The invention provides another technical scheme that: the application of the iron monatomic catalyst in catalytic reduction of nitroarene.
According to some preferred and specific aspects of the invention, said application comprises the steps of: adding nitroaromatic, an iron monatomic catalyst, hydrazine hydrate and a solvent into a reaction vessel, sealing the reaction vessel under the condition of normal pressure and air, reacting at room temperature, after the reaction is finished, centrifugally separating the iron monatomic catalyst, removing the solvent from a solvent phase through rotary evaporation, and purifying a crude product through recrystallization to obtain a target product.
According to some preferred and specific aspects of the invention, in said use, said solvent is ethanol.
According to some preferred and specific aspects of the present invention, in the application, the charging molar ratio of the nitroarene to the hydrazine hydrate is 1: 1-5.
According to some preferable and specific aspects of the invention, in the application, the dosage of the iron monatomic catalyst is 50-100 mg, calculated by the nitroarene, and the nitroarene is 10 mmol.
According to some preferred and specific aspects of the invention, in said use, specific embodiments of said recrystallization are: the crude product is recrystallized and purified by ethanol, the crude product is dissolved in a small amount of boiled ethanol, the mixture is cooled to separate out crystals, and pure target products can be obtained after filtering, alcohol washing and the like.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of an iron monatomic catalyst based on the defects of a catalyst for catalytic reduction of nitroaromatic hydrocarbon in the prior art, the method creatively adopts 2-methylimidazole and amine to be mixed and dispersed in water to form a second solution, then the second solution, ferric salt and zinc nitrate are dispersed in water to prepare a first solution, the first solution and the first solution are mixed and reacted, and a solid intermediate generated by the reaction is calcined, so that the iron monatomic catalyst which is uniform in dispersion of iron monatomic, large in specific surface area and firm in combination and is in the form of an iron-nitrogen co-doped porous carbon material is prepared, and compared with other catalysts for reduction of nitroaromatic hydrocarbon, the prepared iron monatomic catalyst has better activity, more excellent selectivity and stability and high catalytic efficiency; the water is used as a solvent, compared with an organic solvent, the cost is lower, the safety and the environmental protection are higher, and the inventor finds that the product yield of the intermediate can be obviously improved by adopting the water; in addition, the method for preparing the iron monatomic catalyst has the advantages of simple process, cheap and easily-obtained raw materials, mild and environment-friendly conditions and easy large-scale production.
Drawings
FIG. 1 is an SEM photograph of an iron monatomic catalyst prepared in example 1 of the present invention.
FIG. 2 is a TEM image of an iron monatomic catalyst prepared in example 1 of the present invention.
FIG. 3 is an electron micrograph of an iron monatomic catalyst prepared in example 1 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
Example 1 catalyst FeSAPreparation of @ NC-20PhA
The embodiment provides a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) adding 0.1mmol of iron sulfate heptahydrate and 2.0mmol of zinc nitrate hexahydrate into 20mL of water to prepare a first solution; adding 8mmol of 2-methylimidazole and 8mmol of aniline into additional water, and violently stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the stirring second solution, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4h at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing for 2 times, and drying for 12h at 60 ℃;
(2) calcining the solid obtained in the step (1) for 2h at 900 ℃ in a tubular furnace in a nitrogen atmosphere (the heating rate is 5 ℃/min), and obtaining the final iron monatomic catalyst in the form of the iron and nitrogen co-doped porous carbon material, which is recorded as FeSA@ NC-20PhA (where Fe represents an iron atom, SA represents a single atom, NC represents a nitrogen-doped carbon material, PhA represents aniline, and 20 represents a Zn/Fe molar ratio). The obtained iron monatomic catalyst was tested, and SEM images, TEM images and spherical aberration electron microscope images thereof are respectively shown in fig. 1, fig. 2 and fig. 3, the SEM images show that the Fe monatomic catalyst substantially maintained the morphology of the precursor zeolite imidazolate framework materials (ZIFs) thereof, and the particle size was approximately about 100nm, and the TEM images and the spherical aberration electron microscope images show that there were no significant iron nanoparticles in the catalyst, and iron was mainly anchored on the N-doped carbon material in a monoatomic form, which indicates that the iron monatomic catalyst of this example was uniformly dispersed in iron monatomic, had a large specific surface area, and was firmly bonded.
Example 2
The embodiment provides a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) adding 0.1mmol of iron sulfate heptahydrate and 2.0mmol of zinc nitrate hexahydrate into 20mL of water to prepare a first solution; adding 8mmol of 2-methylimidazole and 4mmol of oleylamine into the other water, and violently stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the stirring second solution, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4h at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing for 2 times, and drying for 12h at 60 ℃;
(2) calcining the solid obtained in the step (1) for 2h at 900 ℃ in a tubular furnace in a nitrogen atmosphere (the heating rate is 5 ℃/min), and obtaining the final iron monatomic catalyst in the form of the iron and nitrogen co-doped porous carbon material, which is recorded as FeSA@ NC-20OA (where Fe represents an iron atom, SA represents a single atom, NC represents a nitrogen-doped carbon material, OA represents oleylamine, and 20 represents a molar ratio of Zn/Fe).
Example 3
The embodiment provides a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) adding 0.1mmol of iron sulfate heptahydrate and 2.0mmol of zinc nitrate hexahydrate into 20mL of water to prepare a first solution; adding 8mmol of 2-methylimidazole and 8mmol of n-butylamine in another water, and violently stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the stirring second solution, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4h at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing for 2 times, and drying for 12h at 60 ℃;
(2) calcining the solid obtained in the step (1) for 2h at 900 ℃ in a tubular furnace in a nitrogen atmosphere (the heating rate is 5 ℃/min), and obtaining the final iron monatomic catalyst in the form of the iron and nitrogen co-doped porous carbon material, which is recorded as FeSA@ NC-20BuA (where Fe represents an iron atom, SA represents a single atom, NC represents a nitrogen-doped carbon material, BuA represents n-butylamine, and 20 represents a Zn/Fe molar ratio).
Example 4
The embodiment provides a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) adding 0.1mmol of iron sulfate heptahydrate and 2.0mmol of zinc nitrate hexahydrate into 20mL of water to prepare a first solution; adding 8mmol of 2-methylimidazole and 8mmol of benzylamine into additional water, and violently stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the stirring second solution, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4h at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing for 2 times, and drying for 12h at 60 ℃;
(2) calcining the solid obtained in the step (1) for 2h at 900 ℃ in a tubular furnace in a nitrogen atmosphere (the heating rate is 5 ℃/min), and obtaining the final iron monatomic catalyst in the form of the iron and nitrogen co-doped porous carbon material, which is recorded as FeSA@ NC-20BnA (where Fe denotes an iron atom, SA denotes a single atom, NC denotes a nitrogen-doped carbon material, BnA denotes benzylamine, and 20 denotes a Zn/Fe molar ratio).
Comparative example 1
The embodiment provides a preparation method of an iron monatomic catalyst, which comprises the following steps:
(1) adding 0.1mmol of iron sulfate heptahydrate and 2.0mmol of zinc nitrate hexahydrate into 20mL to prepare a first solution; adding 8mmol of 2-methylimidazole into the other water, and stirring vigorously for 10min until the mixture is stirred uniformly to obtain a second solution; then pouring the first solution into the stirring second solution, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, and after the reaction is finished;
(2) and adding 8mmol of aniline into the mixed solution after reaction, preserving the temperature and reacting for 3h, after the reaction is finished, centrifugally separating the obtained solid, washing for 2 times, and drying at 60 ℃ for 12 h. The solid thus obtained was calcined in a tube furnace at 900 ℃ for 2h under a nitrogen atmosphere (rate of temperature rise 5 ℃/min).
The ZIF obtained by the method is of a massive sheet structure, and the carbon material obtained by high-temperature sintering is small in specific surface area and uneven in distribution of iron elements.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: aniline was replaced with an equimolar amount of dicyandiamide. The ZIF obtained by the method is of a massive sheet structure, and the carbon material obtained by high-temperature sintering is small in specific surface area and uneven in distribution of iron elements.
Examples 5-26 reduction of nitroarenes
10mmol of nitroarene having the structure shown in Table 1 below, 100mg of Fe prepared in example 1SA@ NC-20PhA, 30mmol of hydrazine hydrate, 10mL of methanol plusPutting the mixture into a reaction vessel, sealing and reacting for 1h at room temperature under the condition of normal pressure and air, after the reaction is finished and the temperature is reduced, centrifugally separating a catalyst and a reaction solution, determining the reaction yield and selectivity through gas phase detection, finally removing the solvent from the reaction solution through rotary evaporation, dissolving a crude product into a small amount of boiled ethanol, cooling to separate out crystals, filtering the ethanol and washing to obtain a pure target product, wherein the specific results are shown in Table 1, wherein
Are all very important pharmaceutical or chemical intermediates.
Application comparative example 1
Basically, the method is the same as the method in example 5, and the method only differs from the method in that: "Fe prepared in example 1SA@ NC-20PhA "was replaced with the catalyst prepared in comparative example 1.
Comparative application example 2
Basically, the method is the same as the method in example 5, and the method only differs from the method in that: "Fe prepared in example 1SA@ NC-20PhA "was replaced with the catalyst prepared in comparative example 2.
TABLE 1
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of an iron monatomic catalyst is characterized by comprising the following steps:
(1) dispersing ferric salt and zinc nitrate in water to prepare a first solution, and dispersing 2-methylimidazole and amine in water to prepare a second solution;
mixing the prepared first solution and the second solution, and reacting to generate a solid intermediate;
(2) and (2) calcining the intermediate obtained in the step (1) in a protective atmosphere to prepare the iron monatomic catalyst in the form of an iron-nitrogen co-doped porous carbon material.
2. The method for preparing an iron monatomic catalyst according to claim 1, wherein in the step (1), the amine is one or a combination of more selected from aniline, oleylamine, n-butylamine, and benzylamine.
3. The method for preparing the iron monatomic catalyst according to claim 1, wherein in the step (1), the iron salt is one or more selected from the group consisting of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous phosphate, and the zinc nitrate is zinc nitrate hexahydrate.
4. The method for preparing the iron monatomic catalyst according to claim 1, wherein in the step (1), the molar ratio of the iron salt to the zinc nitrate to the amine to the 2-methylimidazole is 1:10 to 30:40 to 120.
5. The method for preparing an iron monatomic catalyst according to claim 1, wherein in the step (1), the first solution is added to the second solution under stirring, and the mixture is stirred, mixed and reacted.
6. The method for preparing an iron monatomic catalyst according to claim 1, wherein in the step (1), the reaction is carried out at a temperature of 25 to 50 ℃.
7. The method for preparing an iron monatomic catalyst according to claim 1, wherein in the step (2), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere; and/or in the step (2), the calcination is carried out at 800-1000 ℃; and/or in the step (2), in the calcining process, the temperature rising rate is 5-15 ℃/min, and the calcining time is 2-4 h.
8. An iron monatomic catalyst produced by the production method according to any one of claims 1 to 7, which is in the form of an iron-nitrogen-codoped porous carbon material.
9. Use of the iron monatomic catalyst according to claim 8 for the catalytic reduction of nitroarenes.
10. The application according to claim 9, characterized in that it comprises the following steps: adding nitroaromatic, an iron monatomic catalyst, hydrazine hydrate and a solvent into a reaction vessel, sealing the reaction vessel under the condition of normal pressure and air, reacting at room temperature, after the reaction is finished, centrifugally separating the iron monatomic catalyst, removing the solvent from a solvent phase through rotary evaporation, and purifying a crude product through recrystallization to obtain a target product.
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