CN112354552A - Preparation method of cheap transition metal and nitrogen co-doped porous carbon material - Google Patents

Preparation method of cheap transition metal and nitrogen co-doped porous carbon material Download PDF

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CN112354552A
CN112354552A CN201910671438.5A CN201910671438A CN112354552A CN 112354552 A CN112354552 A CN 112354552A CN 201910671438 A CN201910671438 A CN 201910671438A CN 112354552 A CN112354552 A CN 112354552A
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陆国平
徐家贤
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Nanjing University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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Abstract

The invention discloses a preparation method of a cheap transition metal and nitrogen co-doped porous carbon material. According to the method, amine is added into a water phase to regulate the particle size and morphology of ZIFs, and then the amine modified zeolite imidazole ester framework material is calcined at high temperature to finally obtain the cheap transition metal and nitrogen co-doped nano porous carbon material. The method has the advantages of simple and effective process, environmental protection and safety, cheap and easily obtained raw materials, easy amplification production, large specific surface area of the prepared carbon material, good dispersibility, uniform distribution of cheap transition metal nanoparticles, excellent catalytic performance for hydroxymethylfurfural oxidation esterification reaction and oxygen reduction reaction, and application prospect in the fields of organic catalysis, biomass conversion, electrocatalysis, energy storage and the like.

Description

Preparation method of cheap transition metal and nitrogen co-doped porous carbon material
Technical Field
The invention belongs to the field of preparation of nano porous materials, and relates to a preparation method of a low-cost transition metal and nitrogen co-doped porous carbon material.
Background
Due to the excellent oxidation-reduction performance, good conductivity and high chemical stability of the cheap transition metal and nitrogen co-doped porous carbon material, the material has good application prospect in the fields of organic synthesis, photoelectrocatalysis and energy. The conventional method for synthesizing the material is achieved by carbonizing a mixture of natural products (or polymers) and cheap transition metal salts (angelw. chem. int. ed.2017,56,11242; Science 2011,332,443). However, these methods cannot form ordered porous precursors, and thus the obtained carbon materials mostly only have amorphous structures, have large particles and uneven pore size distribution, and influence the application value of the carbon materials in some specific fields, such as hydroxymethylfurfural oxidative esterification and oxygen reduction.
Most of the cheap transition metals and nitrogen-codoped porous carbon materials at present need high-temperature and high-pressure reaction conditions for catalyzing the hydroxymethylfurfural oxidation and esterification reaction, and the catalyst stability is poor (ChemCatchem 2016,8, 2907; ChemSuschem 2014,7, 3334). Most of cheap transition metals and nitrogen-codoped porous carbon materials have low overpotential and limiting current for catalyzing oxygen reduction reaction, and the stability needs to be further improved (J.Mater.chem.A 2017,5, 18933; J.Mater.chem.A 2018,6, 5740).
In recent years, zeolite imidazolate framework materials (ZIFs) have become one of the most ideal precursors for synthesizing cheap transition metal and nitrogen co-doped porous carbon materials due to their mild synthesis conditions, high nitrogen content, and ordered and controllable pore structures (j. In order to solve the problems of agglomeration of metal particles and collapse of ZIFs structures in the ZIFs carbonization process, a dragon task group utilizes zinc as a self-sacrificial template, and can prepare a cheap transition metal and nitrogen co-doped porous carbon material (adv. mater.2015,27,5010) with uniformly distributed metal particles and larger specific surface area. However, the ZIFs of this method need to be prepared in methanol solution, with low yield and large particle size.
Disclosure of Invention
The invention aims to provide a preparation method of a cheap transition metal and nitrogen co-doped porous carbon material, which has the advantages of simple process, easiness in large-scale production, uniform distribution of cheap transition metal nanoparticles and large specific surface area.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the cheap transition metal and nitrogen co-doped porous carbon material (M @ CN-Y-X) comprises the following steps of firstly adding amine into a water phase to regulate the particle size and the morphology of ZIFs, and then carrying out high-temperature pyrolysis on the amine modified ZIFs to finally obtain the nano porous carbon material:
step 1, adding a mixed solution of cheap transition metal salt and zinc nitrate hexahydrate into a mixed solution of 2-methylimidazole and amine under stirring, carrying out stirring reaction, carrying out centrifugal separation, washing with water, and drying to obtain a ZIF precursor;
and 2, calcining the ZIF precursor at the high temperature of 900 +/-100 ℃ in a nitrogen atmosphere to obtain the low-price transition metal and nitrogen co-doped porous carbon material, which is marked as M @ CN-Y-X (wherein M represents a low-price transition metal atom, Y represents amine, and X represents the molar ratio of Zn to M).
Preferably, in the step 1, the molar ratio of the cheap transition metal salt, zinc nitrate hexahydrate and amine to 2-methylimidazole is 1: 2-4: 12: 12.
Preferably, in the step 1, the reaction temperature is 25-50 ℃ and the reaction time is 2-8 h.
Preferably, in step 1, the cheap transition metal salt is selected from cobalt nitrate hexahydrate, nickel nitrate hexahydrate, manganese chloride tetrahydrate or copper acetate monohydrate.
Preferably, in step 1, the amine is selected from aniline (PhA), Oleylamine (OA), n-butylamine (nBuA), benzylamine (BnA), dabco (da) or Diethanolamine (DEA).
Preferably, in the step 2, the temperature rise rate during high-temperature calcination is 5-15 ℃/min, and the calcination time is 2-4 h.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the method has the advantages of simple process, cheap and easily-obtained raw materials, mild and environment-friendly conditions and easy amplification production.
(2) In the method, the amine is used as a coordination regulator, and the coordination capability of different crystal faces of the amine and ZIFs can be changed by changing the type of the amine, so that the particle size and the morphology of the material are regulated. In addition, Zn can be vaporized under the high-temperature condition, and the specific surface area of the material, the distribution of metal nano particles and the particle size can be controlled by regulating the proportion of the cheap transition metal and the zinc, so that the performance of the catalyst is regulated. Finally, different types of metal and nitrogen co-doped porous carbon materials can be obtained by changing the metal types, and the catalytic performance of the material is adjusted based on the self properties of different cheap transition metals. The prepared porous carbon material has excellent catalytic performance on hydroxymethylfurfural oxidation esterification reaction and oxygen reduction reaction.
Drawings
FIG. 1 is a polarization diagram of an oxygen reduction reaction.
FIG. 2 is a voltammogram of an oxygen reduction cycle.
FIG. 3 is an SEM photograph of Co @ CN-PhA-3 prepared in example 1.
FIG. 4 is a TEM image of Co @ CN-PhA-3 prepared in example 1.
FIG. 5 is an SEM photograph of Co @ CN-OA-3 obtained in example 2.
FIG. 6 is a TEM image of Co @ CN-OA-3 obtained in example 2.
FIG. 7 is an SEM photograph of Co @ CN-DEA-3 obtained in example 3.
FIG. 8 is a TEM image of Co @ CN-DEA-3 obtained in example 3.
FIG. 9 is an SEM photograph of Co @ CN-BnA-3 obtained in example 4.
FIG. 10 is a TEM image of Co @ CN-BnA-3 obtained in example 4.
FIG. 11 is an SEM photograph of Cu @ CN-PhA-3 prepared in example 5.
FIG. 12 is a TEM image of Cu @ CN-PhA-3 prepared in example 5.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1: preparation of catalyst Co @ CN-PhA-3
0.5mmol of cobalt nitrate hexahydrate and 1.5mmol of zinc nitrate hexahydrate are added into 20mL of water to prepare a solution (solution 1). 8mmol of 2-methylimidazole and 8mmol of aniline (PhA) were added to additional water and stirred vigorously for 10min until the mixture was stirred well (solution 2). Solution 1 is poured into stirring solution 2 and the resulting suspension is stirred for a further period of time. After stirring, centrifugation was carried out, and the solid obtained by separation was washed 2 times with water and dried at 60 ℃ for 12 hours. And calcining the dried solid at 900 ℃ for 2h in a tubular furnace in a nitrogen atmosphere at the temperature rise rate of 5 ℃/min to obtain the cobalt and nitrogen Co-doped porous carbon material which is marked as Co @ CN-PhA-3 (wherein Co represents a cobalt atom, PhA represents aniline, and 3 represents the molar ratio of Zn to Co). As shown in fig. 3 and 4, the SEM and TEM images of the carbon material showed a particle size of about 100nm, a uniform particle size distribution, and a small particle size of cobalt nanoparticles in the carbon material.
Example 2: preparation of catalyst Co @ CN-OA-3
This example is essentially the same as example 1, except that the amine used was Oleylamine (OA) and the carbon material was noted as Co @ CN-OA-3. An SEM image and a TEM image are respectively shown in fig. 5 and fig. 6, the carbon material has a particle size of 100-200 nm, a layer of carbon film is coated outside the particles (the carbon film is an oleylamine carbonized structure coated on the surface of ZIFs), and cobalt nanoparticles in the carbon material have small particle size and are uniformly distributed.
Example 3: preparation of catalyst Co @ CN-DEA-3
This example is essentially the same as example 1, except that the amine used is Diethanolamine (DEA) and the carbon material is designated Co @ CN-DEA-3. As shown in fig. 7 and 8, the SEM image and the TEM image of the carbon material are respectively shown, and the carbon material has a sheet-like structure, and the cobalt nanoparticles inside the carbon material have a small particle size and are uniformly distributed.
Example 4: preparation of catalyst Co @ CN-BnA-3
This example is essentially the same as example 1, except that the amine used was benzylamine (BnA) and the carbon material was noted as Co @ CN-DEA-3. As shown in the SEM images and TEM images of the carbon material respectively in FIGS. 9 and 10, the carbon material is particles with a particle size of 500-1000 nm, and the cobalt nanoparticles in the carbon material have a large particle size and a small content.
Example 5: preparation of catalyst Cu @ CN-PhA-3
This example is essentially the same as example 1, except that inexpensive transition metal salts such as copper acetate monohydrate and zinc nitrate hexahydrate are used, the carbon material being designated as Cu @ CN-PhA-3. The SEM images and TEM images are shown in fig. 11 and 12, respectively, and the carbon material is particles having a particle size of 100nm, and no copper particles are evident inside the carbon material.
Example 6: preparation of the other catalyst M @ CN-Y-X
0.5mmol of cheap metal salt and 1.5mmol of zinc nitrate hexahydrate are added into 20mL of water to prepare a solution (solution 1). 8mmol of 2-methylimidazole and 8mmol of amine were added to additional water and stirred vigorously for 10min until the mixture was stirred well (solution 2). Solution 1 is poured into stirring solution 2 and the resulting suspension is stirred for a further period of time. After stirring, centrifugation was carried out, and the solid obtained by separation was washed 2 times with water and dried at 60 ℃ for 12 hours. And calcining the dried solid at 900 ℃ for 2h in a tubular furnace under the nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and obtaining the cheap metal and nitrogen co-doped porous carbon material which is marked as M @ CN-Y-X (wherein M represents a metal atom, Y represents aniline, and X represents the molar ratio of Zn to M).
Example 7: oxidative esterification of HMF
0.25mmol of HMF, 10mg of Co @ CN-Y-X and 2mL of methanol are added into a reaction vessel and reacted for 24 hours at room temperature under the condition of normal pressure and air. And after the reaction is finished and the temperature is reduced, centrifugally separating the catalyst and the reaction liquid, and determining the reaction yield and selectivity by gas phase detection. And finally, removing the solvent from the reaction solution through rotary evaporation, and purifying the crude product through column chromatography to obtain a target product 5. The reaction results are shown in Table 1, with Co @ CN-PhA-3 and Co @ CN-OA-3 having the best catalytic effects.
TABLE 1 Co @ CN-Y-X catalyzed HMF oxidative esterification reactiona
Figure BDA0002141867380000051
Figure BDA0002141867380000052
aReaction conditions are as follows: catalyst 10mg, HMF 0.2mmol, MeOH 2mL, air, 24h, room temperature;bgas phase yield;cthe dosage of the catalyst is 20mg, and the reaction time is 48 h;dthe catalyst precursor was ZIF-CoZn3-M (M indicates that the solvent used in the preparation of the ZIF was methanol).
Example 8: oxygen reduction reaction
4mg of Co @ CN-PhA-3 was dispersed in 1mL of ethanol and sonicated for 2h to form a uniformly dispersed black ink, 0.04mL of Nafion solution (content 5 wt.%). Co @ CN-PhA-3 is loaded on a 5mm disk glassy carbon electrode as an electrode material in a dropping mode, and the loading amount is 0.2mg/cm2The platinum sheet was used as the counter electrode, the electrolyte was 0.1KOH, and the participating electrode was Ag/AgCl (3.5M KCl solution). The scanning rate of the cyclic voltammetry is 10 mV/s; under the condition of 1600rpm, the scanning rate of the linear scanning voltammetry is 5 mV/s; the stability test conditions were: cyclic voltammetry under oxygen was scanned at a rate of 50mV/s for 5000 cycles between 0.2V and-1.0V. The reaction results are shown in figures 1 and 2, the initial potential of the catalyst Co @ CN-PhA-3 oxygen reduction is 0.93V vs RHE, the half-wave potential is 0.84V, and the limiting diffusion current is 5.86mA/cm2. These data are very close to the 20 wt.% Pt/C performance. Meanwhile, the catalyst has good stability, and after the cyclic voltammetry scans for 5000 circles at the speed of 50mV/s in the range from 0.2V to-1.0V in the oxygen atmosphere, the half-wave potential is only reduced by 7 mV.

Claims (8)

1. The preparation method of the cheap transition metal and nitrogen co-doped porous carbon material is characterized by comprising the following specific steps of:
step 1, adding a mixed solution of cheap transition metal salt and zinc nitrate hexahydrate into a mixed solution of 2-methylimidazole and amine under stirring, carrying out stirring reaction, carrying out centrifugal separation, washing with water, and drying to obtain a ZIF precursor;
and 2, calcining the ZIF precursor at the high temperature of 900 +/-100 ℃ in a nitrogen atmosphere to obtain the low-cost transition metal and nitrogen co-doped porous carbon material.
2. The preparation method according to claim 1, wherein in the step 1, the molar ratio of the cheap transition metal salt, the zinc nitrate hexahydrate and the amine to the 2-methylimidazole is 1: 2-4: 12: 12.
3. The method according to claim 1, wherein the reaction temperature in step 1 is 25 to 50 ℃.
4. The preparation method according to claim 1, wherein in the step 1, the reaction time is 2-8 h.
5. The method according to claim 1, wherein in step 1, the transition metal salt is selected from cobalt nitrate hexahydrate, nickel nitrate hexahydrate, manganese chloride tetrahydrate, and copper acetate monohydrate.
6. The method according to claim 1, wherein in step 1, the amine is selected from aniline, oleylamine, n-butylamine, benzylamine, DABCO, and diethanolamine.
7. The method according to claim 1, wherein in the step 2, the temperature rise rate during the high-temperature calcination is 5 to 15 ℃/min.
8. The preparation method according to claim 1, wherein in the step 2, the calcination time is 2-4 h.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097501A (en) * 2021-03-11 2021-07-09 合肥工业大学 Preparation method of carbon-based catalyst
CN113699554A (en) * 2021-09-17 2021-11-26 中国矿业大学 Preparation method and application of rare earth metal and transition metal co-doped carbon-based material
CN116396249A (en) * 2023-04-11 2023-07-07 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran

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CN106905536A (en) * 2017-02-22 2017-06-30 华南理工大学 A kind of method of the materials of Fast back-projection algorithm multi-stage porous ZIF 8
US20180326397A1 (en) * 2015-11-27 2018-11-15 The Regents Of The University Of California Zeolitic imidazolate frameworks
CN109126849A (en) * 2017-06-28 2019-01-04 中国科学院大连化学物理研究所 A method of preparing the monatomic catalyst of Ni-N-C
CN109675632A (en) * 2018-12-28 2019-04-26 西安交通大学 A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN105985362A (en) * 2015-02-14 2016-10-05 李亚丰 Method for preparing zeolite imidazate framework material
US20180326397A1 (en) * 2015-11-27 2018-11-15 The Regents Of The University Of California Zeolitic imidazolate frameworks
CN106905536A (en) * 2017-02-22 2017-06-30 华南理工大学 A kind of method of the materials of Fast back-projection algorithm multi-stage porous ZIF 8
CN109126849A (en) * 2017-06-28 2019-01-04 中国科学院大连化学物理研究所 A method of preparing the monatomic catalyst of Ni-N-C
CN109675632A (en) * 2018-12-28 2019-04-26 西安交通大学 A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097501A (en) * 2021-03-11 2021-07-09 合肥工业大学 Preparation method of carbon-based catalyst
CN113699554A (en) * 2021-09-17 2021-11-26 中国矿业大学 Preparation method and application of rare earth metal and transition metal co-doped carbon-based material
CN116396249A (en) * 2023-04-11 2023-07-07 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran
CN116396249B (en) * 2023-04-11 2023-11-21 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran

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