CN112495417B - Iron single-atom catalyst and preparation method and application thereof - Google Patents

Iron single-atom catalyst and preparation method and application thereof Download PDF

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CN112495417B
CN112495417B CN202011398097.8A CN202011398097A CN112495417B CN 112495417 B CN112495417 B CN 112495417B CN 202011398097 A CN202011398097 A CN 202011398097A CN 112495417 B CN112495417 B CN 112495417B
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陆国平
杨盟
孙璐
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Jiangsu Liyuan Pharmaceutical Co ltd
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Abstract

The invention discloses an iron monoatomic catalyst, a preparation method and application thereof, 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 first solution with the second solution, and reacting to generate a solid intermediate; (2) Calcining the obtained intermediate in a protective atmosphere to prepare an iron single-atom catalyst in the form of an iron-nitrogen co-doped porous carbon material, wherein the iron single atoms are uniformly dispersed and firmly combined; the iron single-atom catalyst prepared by the method has better activity, better selectivity and stability and high catalytic efficiency compared with other catalysts for the reduction reaction of the nitroaromatic hydrocarbon; meanwhile, the method for preparing the iron single-atom catalyst has the advantages of simple process, low-cost and easily-obtained raw materials, mild and environment-friendly conditions and easy scale-up production.

Description

Iron single-atom catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of monoatomic catalyst preparation, and particularly relates to an iron monoatomic catalyst, a preparation method thereof and application thereof in catalyzing nitroarene reduction.
Background
Arylamine compounds are a very important class of chemical intermediates that find wide application in the synthesis of pharmaceuticals, pesticides, dyes, additives, surfactants, textile assistants, chelating agents, and polymers. Most aromatic amines are produced by reduction of the corresponding nitroaromatic hydrocarbons. The method for reducing nitroarene is a lot, 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 lower. Meanwhile, the method also has the advantages of low efficiency, general use for preparing aromatic amine by reducing special raw materials, and adverse operation and environment caused by the release of harmful gas in the reaction process.
At present, the catalytic reduction of nitroaromatics to aniline is undoubtedly the most efficient method for the selective reduction to aniline today (Applied Catalysis B: environmental 2018,227,386). The method for preparing aniline by catalytic reduction of nitroaromatic hydrocarbon mainly comprises three methods, namely a catalytic hydrogenation reduction method, a hydrazine hydrate reduction method and a 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 waste gas and waste residue generation and the like (Chemistry, an Asian Journal 2017,12,785), and is particularly suitable for the production of short-circuit aromatic amine compounds in small batches. The common catalysts used in hydrazine hydrate reduction are noble metal catalysts such as Pd, pt and Au, and various cheap metal catalysts (Chemical Communications 2016,52,4199;Chemical Communications2011,47,10972;Angewandte Chemie 2012,51,10190;Green Chemistry 2016,18,2435) are developed in recent years by researchers for the method. However, these catalysts have more or less obvious problems such as low catalytic efficiency, poor reaction selectivity, severe reaction conditions, poor substrate tolerance, etc.
The single-atom catalyst has remarkably different activity, selectivity and stability from those of the conventional nano catalyst due to the special structure (Chemical Reviews 2020.10.1021/acs. Chemrev.9b00818.), but at present, there is still no single-atom catalyst for reducing nitroaromatics, and the iron single-atom prepared by the existing methods has an unsatisfactory effect on reducing nitroaromatics, so that efficient catalytic reduction is difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art and providing a preparation method of an iron single-atom catalyst suitable for reducing nitroaromatic hydrocarbon, wherein the iron single-atom catalyst prepared by the method has excellent catalytic performance for nitroaromatic hydrocarbon reduction reaction, mild reaction conditions and good selectivity and substrate tolerance; 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 mass production.
The invention also provides the iron single-atom 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 single-atom catalyst prepared by the method in catalytic reduction of nitroaromatic hydrocarbon.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing an iron monoatomic catalyst, 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 with the second solution, and reacting to generate a solid intermediate;
(2) Calcining the intermediate obtained in the step (1) under a protective atmosphere to prepare the iron single-atom catalyst in the form of an iron-nitrogen co-doped porous carbon material.
In the present invention, the iron monoatomic catalyst is denoted as Fe SA NC-XA, wherein 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 a plurality of aniline, oleylamine, n-butylamine and benzylamine, and the specific amine has better capability of anchoring iron monoatoms than other amine compounds, can be coated on the surfaces of ZIFs, inhibits the growth of ZIFs particles, further forms ZIFs with smaller particle sizes, and is favorable for inhibiting agglomeration of iron atoms in the pyrolysis process so as 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 ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous phosphate.
According to some preferred and specific aspects of the invention, in step (1), the zinc nitrate is zinc nitrate hexahydrate.
According to some preferred aspects of the invention, in step (1), the molar ratio of the iron salt, the zinc nitrate, the amine and the 2-methylimidazole is 1:10 to 30:40 to 120:40 to 120. More preferably, in the step (1), the feeding molar ratio of the ferric salt, the zinc nitrate, the amine and the 2-methylimidazole is 1:15-25:50-100:50-100.
According to the invention, in the step (1), the first solution is added into the second solution under stirring, and the mixture is stirred and mixed for reaction.
According to some preferred aspects of the invention, in step (1), the first solution is added to the second solution under stirring, the resulting suspension is stirred for a further period of time, after the reaction has ended, the resulting solid is separated by centrifugation, washed with water a plurality of times, and dried at 55-65 ℃ for a drying time of 10-14h.
According to some preferred aspects of the invention, in step (1), the reaction is carried out at a temperature of 25 to 50 ℃.
According to some preferred aspects of the invention, in step (2), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
According to some preferred aspects of the invention, in step (2), the calcination is carried out at 800-1000 ℃.
According to some preferred aspects of the invention, in step (2), during the calcination, the temperature rise rate is 5 to 15 ℃/min and the calcination time is 2 to 4 hours.
According to some specific aspects of the invention, the calcination is performed in a tube furnace.
The invention provides another technical scheme that: the iron single-atom 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 single-atom catalyst in catalytic reduction of nitroaromatics.
According to some preferred and specific aspects of the invention, the application comprises the steps of: adding nitroarene, an iron single-atom catalyst, hydrazine hydrate and a solvent into a reaction container, sealing the reaction container at room temperature under the condition of normal pressure air, centrifuging the iron single-atom catalyst after the reaction is finished, 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 the application, the solvent is ethanol.
According to some preferred and specific aspects of the invention, in the application, the feeding molar ratio of the nitroarene to the hydrazine hydrate is 1:1-5.
According to some preferred and specific aspects of the invention, in the application, 10mmol of nitroarene is calculated as nitroarene, and the amount of the iron monoatomic catalyst is 50 to 100mg.
According to some preferred and specific aspects of the invention, in the application, the specific embodiments of the recrystallization are: the crude product is recrystallized and purified by ethanol, the crude product is dissolved in a small amount of boiled ethanol, the crystals are separated out by cooling, and the pure target product can be obtained after the ethanol is filtered and washed.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
based on the defects of the catalyst for catalytic reduction of nitroaromatic hydrocarbon in the prior art, the invention provides a preparation method of an iron single-atom catalyst, which is characterized in that 2-methylimidazole and amine are creatively mixed and dispersed in water to form a second solution, then the second solution is prepared by dispersing ferric salt and zinc nitrate in water, the first solution is mixed and reacted, and then a solid intermediate generated by the reaction is calcined, so that the iron single-atom catalyst which is uniform in iron single-atom dispersion, large in specific surface area and firm in combination and in the form of an iron nitrogen co-doped porous carbon material is prepared, and compared with other catalysts for reduction reaction of the nitroaromatic hydrocarbon, the prepared iron single-atom catalyst has better activity, more excellent selectivity and stability and high catalytic efficiency; compared with an organic solvent, the method has the advantages of lower cost, safety and environmental protection, and the inventor unexpectedly discovers that the adoption of water can also obviously improve the product yield of the intermediate; in addition, the method for preparing the iron single-atom catalyst has the advantages of simple process, low-cost and easily-obtained raw materials, mild and environment-friendly conditions and easy scale-up production.
Drawings
FIG. 1 is an SEM image of an iron single-atom catalyst prepared in example 1 of the invention.
FIG. 2 is a TEM image of the iron monoatomic catalyst prepared in example 1 of the present invention.
FIG. 3 is a spherical aberration electron microscope image of the iron single atom catalyst prepared in example 1 of the present invention.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
In the following, all starting materials are commercially available or prepared by methods conventional in the art, unless otherwise specified.
EXAMPLE 1 catalyst Fe SA Preparation of @ NC-20PhA
The example provides a preparation method of an iron single-atom catalyst, which comprises the following steps:
(1) Adding 0.1mmol of ferric 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 the other water, and vigorously stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the second solution which is being stirred, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing with water for 2 times, and drying for 12 hours at 60 ℃;
(2) Calcining the solid obtained in the step (1) for 2 hours at 900 ℃ in a nitrogen atmosphere in a tube furnace (the heating rate is 5 ℃/min) to obtain the final iron and nitrogen co-doped porous carbon material type iron monoatomic catalyst which is marked as Fe SA 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 the Zn/Fe molar ratio). The obtained iron monoatomic catalyst is tested as shown in an SEM image, a TEM image and a spherical aberration electron microscope image respectively shown in fig. 1, 2 and 3, wherein the SEM image shows that the Fe monoatomic catalyst basically keeps the morphology of a precursor zeolite imidazole ester skeleton structure material (ZIFs), the particle size is about 100nm, the TEM image and the spherical aberration electron microscope image show that no obvious iron nano particles exist in the catalyst, iron is mainly anchored on an N-doped carbon material in a monoatomic form, and the iron monoatomic catalyst prepared by the method has uniform iron monoatomic dispersion, large specific surface area and firm combination.
Example 2
The example provides a preparation method of an iron single-atom catalyst, which comprises the following steps:
(1) Adding 0.1mmol of ferric 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 oil amine into additional water, and vigorously stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the second solution which is being stirred, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing with water for 2 times, and drying for 12 hours at 60 ℃;
(2) Calcining the solid obtained in the step (1) for 2 hours at 900 ℃ in a nitrogen atmosphere in a tube furnace (the heating rate is 5 ℃/min) to obtain the final iron and nitrogen co-doped porous carbon material type iron monoatomic catalyst which is marked as Fe SA 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 the Zn/Fe molar ratio).
Example 3
The example provides a preparation method of an iron single-atom catalyst, which comprises the following steps:
(1) Adding 0.1mmol of ferric 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 into the other water, and vigorously stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the second solution which is being stirred, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing with water for 2 times, and drying for 12 hours at 60 ℃;
(2) Calcining the solid obtained in the step (1) for 2 hours at 900 ℃ in a nitrogen atmosphere in a tube furnace (the heating rate is 5 ℃/min) to obtain the final iron and nitrogen co-doped porous carbon material type iron monoatomic catalyst which is marked as Fe SA NC-20BuA (wherein 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 example provides a preparation method of an iron single-atom catalyst, which comprises the following steps:
(1) Adding 0.1mmol of ferric 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 the other water, and vigorously stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the second solution which is being stirred, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, after the reaction is finished, centrifugally separating the obtained solid, washing with water for 2 times, and drying for 12 hours at 60 ℃;
(2) Calcining the solid obtained in the step (1) for 2 hours at 900 ℃ in a nitrogen atmosphere in a tube furnace (the heating rate is 5 ℃/min) to obtain the final iron and nitrogen co-doped porous carbon material type iron monoatomic catalyst which is marked as Fe SA NC-20BnA (wherein Fe represents an iron atom, SA represents a single atom, NC represents a nitrogen-doped carbon material, bnA represents benzylamine, and 20 represents the Zn/Fe molar ratio).
Comparative example 1
The example provides a preparation method of an iron single-atom catalyst, which comprises the following steps:
(1) Adding 0.1mmol of ferric 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 vigorously stirring for 10min until the mixture is uniformly stirred to obtain a second solution; then pouring the first solution into the second solution which is being stirred, continuously stirring the obtained suspension for a period of time, mixing, reacting for 4 hours at 25 ℃, and after the reaction is finished;
(2) Then adding 8mmol of aniline into the mixture after reaction, preserving heat for 3 hours, centrifuging the obtained solid after the reaction, washing 2 times, and drying at 60 ℃ for 12 hours. The solid obtained was calcined at 900℃for 2h (heating rate 5℃per minute) in a nitrogen atmosphere in a tube furnace.
The ZIF obtained by the method is of a large-block flaky structure, the specific surface area of the carbon material obtained by high-temperature sintering is small, and the iron element is unevenly distributed.
Comparative example 2
Substantially the same as in example 1, the only difference is that: aniline was replaced with an equivalent molar amount of dicyandiamide. The ZIF obtained by the method is of a large-block flaky structure, the specific surface area of the carbon material obtained by high-temperature sintering is small, and the iron element is unevenly distributed.
EXAMPLES 5-26 reduction of nitroaromatic hydrocarbons
10mmol of nitroarene having the structure shown in Table 1 below, 100mg of Fe prepared in example 1, were reacted SA Adding 10mL of methanol into a reaction vessel, sealing and reacting for 1h at room temperature under normal pressure and air condition, centrifuging to separate a catalyst and a reaction liquid after the reaction is completed, determining reaction yield and selectivity through gas phase detection, removing a solvent from the reaction liquid through rotary evaporation, dissolving a crude product into a small amount of boiled ethanol, cooling to separate out crystals, filtering and washing the crystals to obtain a pure target product, wherein the specific results are shown in table 1, wherein
Figure BDA0002816017500000071
Figure BDA0002816017500000072
Are all very important pharmaceutical or chemical intermediates.
Comparative example 1 was used
Substantially the same as in example 5, the only difference is that: fe prepared in example 1 SA @ NC-20PhA "was replaced with the catalyst prepared in comparative example 1.
Comparative example 2 was used
Substantially the same as in example 5, the only difference is that: fe prepared in example 1 SA @ NC-20PhA "was replaced with the catalyst prepared in comparative example 2.
TABLE 1
Figure BDA0002816017500000073
Figure BDA0002816017500000081
Figure BDA0002816017500000091
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the iron single-atom catalyst is characterized by comprising the following steps of:
(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, wherein the amine is one or a combination of more selected from aniline, oleylamine, n-butylamine and benzylamine;
mixing the prepared first solution with the second solution, and reacting to generate a solid intermediate;
(2) Calcining the intermediate obtained in the step (1) under a protective atmosphere to prepare the iron single-atom catalyst in the form of an iron-nitrogen co-doped porous carbon material.
2. The method for producing an iron monoatomic catalyst according to claim 1, wherein in step (1), the iron salt is one or a combination of more selected from the group consisting of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous phosphate, and the zinc nitrate is zinc nitrate hexahydrate.
3. The method for producing an iron monoatomic catalyst according to claim 1, wherein in 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 120:40 to 120.
4. The method for producing an iron monoatomic catalyst according to claim 1, wherein in step (1), the first solution is added to the second solution under stirring, and the mixture is stirred and reacted.
5. The method for preparing an iron monoatomic catalyst according to claim 1, wherein in step (1), the reaction is carried out at a temperature of 25 to 50 ℃.
6. The method for producing an iron single-atom catalyst according to claim 1, wherein in the step (2), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
7. The method for preparing an iron monoatomic catalyst according to claim 1, wherein in step (2), the calcination is performed at 800 to 1000 ℃; and/or in the step (2), in the calcining process, the heating rate is 5-15 ℃/min, and the calcining time is 2-4 h.
8. An iron monoatomic catalyst made by the method of any one of claims 1 to 7, in the form of an iron nitrogen co-doped porous carbon material.
9. Use of the iron monoatomic catalyst according to claim 8 for the catalytic reduction of nitroaromatics.
10. The application according to claim 9, characterized in that it comprises the steps of: adding nitroarene, an iron single-atom catalyst, hydrazine hydrate and a solvent into a reaction container, sealing the reaction container at room temperature under the condition of normal pressure air, centrifuging the iron single-atom catalyst after the reaction is finished, 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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CN115845892B (en) * 2022-06-27 2024-08-06 海南华瑞医药有限公司 N, S co-doped carbon material loaded zinc monoatom and preparation method and application thereof
CN115124478A (en) * 2022-06-27 2022-09-30 海南华瑞医药有限公司 Iron-nitrogen co-doped carbon material catalyst and application thereof in synthesis of quinazoline and derivatives thereof
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CN115155640B (en) * 2022-07-19 2023-09-05 海南华瑞医药有限公司 Molybdenum catalyst, catalytic composition and application thereof in preparation of amine compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109939718A (en) * 2019-04-15 2019-06-28 中国科学院化学研究所 A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity
CN111036237A (en) * 2019-12-26 2020-04-21 中国科学院山西煤炭化学研究所 Hydrogenation catalyst, preparation method and application thereof
CN111477889A (en) * 2020-06-02 2020-07-31 浙江大学 Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof
CN111727170A (en) * 2018-02-13 2020-09-29 加兹纳特股份公司 Fe-N-C catalyst, preparation method and application thereof
CN111875808A (en) * 2020-07-02 2020-11-03 华侨大学 Nano zeolite imidazole framework material and CO2Auxiliary preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110483787B (en) * 2019-03-12 2020-08-04 中国石油大学(北京) Zeolite imidazate framework material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111727170A (en) * 2018-02-13 2020-09-29 加兹纳特股份公司 Fe-N-C catalyst, preparation method and application thereof
CN109939718A (en) * 2019-04-15 2019-06-28 中国科学院化学研究所 A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity
CN111036237A (en) * 2019-12-26 2020-04-21 中国科学院山西煤炭化学研究所 Hydrogenation catalyst, preparation method and application thereof
CN111477889A (en) * 2020-06-02 2020-07-31 浙江大学 Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof
CN111875808A (en) * 2020-07-02 2020-11-03 华侨大学 Nano zeolite imidazole framework material and CO2Auxiliary preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Heterogeneous Atomic Catalysts Overcoming the Limitations of Single-Atom Catalysts;Hojin Jeong 等;《ACS NANO》;20201103;第14卷;第14355-14374页 *
N掺杂多孔碳材料研究进展;余正发等;《化工进展》;20130405(第04期);第824-831、862页 *
The synergistic catalysis on Co nanoparticles and CoNx sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF;Tao Rui 等;《Chinese Chemical Letters》;20200622;第32卷;第685–690页 *

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