CN114768848B - Preparation method of high-load single-atom catalyst based on zeolite imidazole ester skeleton-67/yeast composite structure - Google Patents
Preparation method of high-load single-atom catalyst based on zeolite imidazole ester skeleton-67/yeast composite structure Download PDFInfo
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Abstract
The invention belongs to the technical field of functional material chemistry and carbon-based nano materials, and particularly relates to a preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure. The method of the invention takes edible yeast cells as mineralizer and host to selectively absorb and chelate Co at fixed points 2+ And (3) ions, then, combining with 2-methylimidazole to form a zeolite imidazole ester skeleton-67/yeast composite structure, and performing heat treatment in an inert atmosphere to form the high-load Co-N-C single-atom catalyst. According to the invention, the zeolite imidazole ester skeleton-67/yeast composite structure is adopted to anchor transition metal ions in a bidirectional manner to increase active sites, and the Co-N-C single-atom catalyst is formed by heat treatment, so that the active atom load capacity of Co-N-C can be remarkably improved, and theoretical basis and technical support are provided for the preparation of the high-load Co-N-C single-atom catalyst.
Description
Technical Field
The invention belongs to the technical field of functional material chemistry and carbon-based nano materials, and particularly relates to a preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure.
Background
The carbon-supported single-atom catalyst with a Co-N-C stable structure is formed by linking Co atoms and a carbon matrix through nitrogen atoms, has the advantage of 100% of active atom utilization rate, and is expected to improve the catalytic performance by improving the active atom loading capacity.
At present, the Co atom loading of the catalyst prepared by the conventional methods such as a space limitation method, a defect control method and the like is mostly distributed in the range of 2-3.5 wt%. In the existing research, the loading capacity of the prepared single-atom catalyst can be improved to about 5wt% based on the zeolite imidazole ester skeleton-67 coordination structure functionalization treatment. However, the single-atom catalysts of the prior art still have the problem of low active atom loadings.
Disclosure of Invention
In order to solve the problem of low active atom load of the single-atom catalyst in the prior art, the invention provides a preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure, and the method can obviously improve the active atom load of Co-N-C.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the high-load single-atom catalyst based on the zeolite imidazole ester skeleton-67/yeast composite structure comprises the following steps:
(1) Activating and culturing yeast cells;
preferably: the mass ratio is 1:1, weighing dry yeast powder and glucose, placing in a beaker, adding deionized water, culturing for 1h under the water bath condition of 37 ℃, and centrifugally washing for 3-5 times to obtain activated yeast;
(2) Transferring the yeast subjected to the activation culture in the step (1) into Co (NO) 3 ) 2 ·6H 2 Adsorption/absorption of Co in O solution 2+ Ion adsorption/absorption for a certain time, continuously adding 2-methylimidazole, vigorously stirring for 5min, standing for aging for 24h, centrifugally washing for 3-5 times, and drying to obtain a precursor A;
(3) Performing heat treatment on the precursor A prepared in the step (2) to prepare a precursor B;
(4) And (3) acidizing the precursor B prepared in the step (3), washing off redundant transition metal simple substances, washing and drying to obtain the monoatomic catalyst.
Preferably, co (NO) as described in step (2) 3 ) 2 ·6H 2 The concentration of the O solution is 0.01-0.3M, so that the yeast cells can be ensured to be capable of effectively absorbing metal ions and keeping the activity of the cells.
Preferably, the adsorption/absorption time in the step (2) is 0.5-2.5 h.
Preferably, the concentration of the 2-methylimidazole solution in the step (2) is 0.08-2.4M, so that the precursor A is ensured to have a composite structure of closely growing zeolite imidazole ester skeleton-67 nano-sheets on the surface of yeast cells.
Preferably, the drying in step (2) is freeze drying, which ensures that the morphology of precursor a is not destroyed and an open cell structure is formed.
Preferably, the heating rate in the step (3) is 3-10 ℃/min, so that the regular structure of the precursor B is ensured; further preferably 3 to 5 ℃/min.
Preferably, the heat treatment temperature in the step (3) is 300-900 ℃, so that the regular structure of the precursor B is ensured; further preferably 600 to 800 ℃.
Preferably, the heat preservation time in the step (3) is 1-5 h, so that the heat treatment is ensured to be sufficient; more preferably 2 to 4 hours.
Preferably, the acid used in the acidification treatment in the step (4) is dilute H 2 SO 4 Or HCl solution, the preferable concentration is 0.3-0.7M, ensuring that the morphology and structure of the catalyst are not damaged;
preferably, the acidification treatment time in the step (4) is 3-12 hours, so that the removal of the metal nano particles is ensured; further preferably 3 to 5 hours.
Advantageous effects
The invention discloses a preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure, which takes edible yeast cells as mineralizers and hosts to selectively absorb and site-specific chelate Co 2+ And (3) ions, then, combining with 2-methylimidazole to form a zeolite imidazole ester skeleton-67/yeast composite structure, and performing heat treatment in an inert atmosphere to form the high-load Co-N-C single-atom catalyst. According to the invention, the zeolite imidazole ester skeleton-67/yeast composite structure is adopted to anchor transition metal ions in a bidirectional manner to increase active sites, and Co-N-C single-atom catalyst is formed by heat treatment, so that the active atom load of Co-N-C can be remarkably improved, and the active atom load of Co of the single-atom catalyst is improved to 12-18 wt%. Provides theoretical basis and technical support for preparing the high-load Co-N-C single-atom catalyst.
Drawings
FIG. 1 is an SEM image of culture activated yeast cells according to example 1 of the present invention;
FIG. 2 is an SEM image of a precursor A prepared according to example 1 of the present invention;
FIG. 3 is an XRD pattern of precursor B and catalyst prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a catalyst prepared according to example 1 of the invention;
fig. 5 is a TEM image of the catalyst prepared in example 1 of the present invention.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
A preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure comprises the following steps:
(1) Activating cultured yeast cells, and culturing the activated yeast cells, wherein SEM images of the activated yeast cells are shown in FIG. 1, and the activated yeast cells are round and full spherical particles with the particle size of about 2 um;
(2) Transferring the yeast subjected to the activation culture in the step (1) into 0.084M Co (NO) 3 ) 2 ·6H 2 Adsorption/absorption of Co in O solution 2+ Ion adsorption/absorption time is 2h, adding 0.672M 2-methylimidazole continuously, stirring vigorously for 5min, standing and aging for 24h, centrifuging and washing for 3 times, drying to obtain a precursor A, wherein an SEM image of the precursor A is shown in FIG. 2, and it can be seen from FIG. 2 that the ZIF-67 on the surface of the yeast cell is compounded with the yeast cell in a sheet structure;
(3) Performing heat treatment on the precursor A prepared in the step (2), and raising the temperature from room temperature to 700 ℃ in argon according to the heating rate of 5 ℃/min, and preserving the temperature for 3 hours to prepare a precursor B, wherein the XRD pattern of the precursor B is shown in figure 3;
(4) And (3) acidizing the precursor B prepared in the step (3) by using 0.5M HCl solution for 4. 4h, and washing off excessive transition metal simple substances. Washing and drying to obtain the single-atom catalyst.
The XRD patterns of the catalyst are shown in FIG. 3, and it can be seen from FIG. 3 that the prepared sample is a carbon-supported cobalt monoatomic catalyst.
The SEM diagram of the catalyst is shown in figure 4, and the prepared catalyst can be seen from figure 4 to keep the zeolite imidazole ester skeleton-67/yeast composite structure, which is beneficial to improving the stability of the catalyst.
A TEM image of the catalyst is shown in fig. 5, and a brighter cobalt monoatomic image can be seen from fig. 5.
The single-atom catalyst Co activity atom loading was 12.789 wt% as measured using inductively coupled plasma atomic emission spectroscopy, and the Co atom loading test data are shown in table 1 below.
Table 1. Co atom loading test data.
| Mass m 0 (g) | Volume V of constant volume 0 (mL) | Test solution element concentration C 0 (mg/L) | Dilution factor f | Concentration of element in digestion solution/original sample solution C 1 (mg/L) | Sample element content C x (mg/ kg) | Sample element content W (wt%) |
| 0.0318 | 10 | 3.87 | 100 | 387.29 | 121788.68 | 12.1789 |
Example 2
A preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure comprises the following steps:
(1) Activating and culturing yeast cells;
(2) Transferring the yeast activated and cultured in the step (1) into Co (NO) of 0.112M 3 ) 2 ·6H 2 Adsorption/absorption of Co in O solution 2+ Ion adsorption/absorption time is 2h, continuously adding 0.896M 2-methylimidazole, vigorously stirring for 5min, standing for aging for 24h, centrifugally washing for 3 times, and drying to obtain a precursor A;
(3) Performing heat treatment on the precursor A prepared in the step (2), and heating the precursor A to 700 ℃ from room temperature in argon according to a heating rate of 5 ℃/min, and preserving heat for 3 hours to prepare a precursor B;
(4) And (3) acidizing the precursor B prepared in the step (3) by using an HCl solution of 0.5 and M for 4: 4h, and washing off excessive transition metal simple substances. Washing and drying to obtain the single-atom catalyst.
The resulting single-atom catalyst Co had an active atom loading of 18.031 wt%.
Example 3
A preparation method of a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure comprises the following steps:
(1) Activating and culturing yeast cells;
(2) Transferring the yeast activated and cultured in the step (1) into Co (NO) of 0.14M 3 ) 2 ·6H 2 Adsorption/absorption of Co in O solution 2+ Ion adsorption/absorption time is 2h, 2-methylimidazole with the concentration of 1.12M is continuously added, the mixture is vigorously stirred for 5min, and the mixture is kept stand and aged for 24h, centrifugally washed for 3 times, and dried to obtain a precursor A;
(3) Performing heat treatment on the precursor A prepared in the step (2), and heating the precursor A to 700 ℃ from room temperature in argon according to a heating rate of 5 ℃/min, and preserving heat for 3 hours to prepare a precursor B;
(4) And (3) acidizing the precursor B prepared in the step (3) by using 0.5M HCl solution for 4. 4h, and washing off excessive transition metal simple substances. Washing and drying to obtain the single-atom catalyst.
The resulting single-atom catalyst Co had an active atom loading of 16.327 wt%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (4)
1. The preparation method of the high-load single-atom catalyst based on the zeolite imidazole ester skeleton-67/yeast composite structure is characterized by comprising the following steps of:
(1) Activating and culturing yeast cells to obtain activated yeast for later use;
(2) Transferring the activated yeast obtained in the step (1) into Co (NO) 3 ) 2 ·6H 2 Adsorption/absorption of Co in O solution 2+ After ion adsorption/absorption for a period of time, 2-methylimidazole is continuously added, and the mixture is stirred vigorously, kept stand for aging and centrifugally washedDrying to obtain a precursor A;
(3) Performing heat treatment on the precursor A prepared in the step (2) to prepare a precursor B;
(4) Acidifying the precursor B prepared in the step (3), and then washing and drying to obtain the monoatomic catalyst;
in the step (2), the adsorption/absorption time is 0.5-2.5 h, standing and ageing are carried out for 24h, centrifugal washing is carried out for 3-5 times, and the drying is freeze drying;
in step (2), the Co (NO) 3 ) 2 ·6H 2 The concentration of the O solution is 0.01-0.3M, and the concentration of the 2-methylimidazole is 0.08-2.4M;
in the step (3), the heat treatment specifically includes: raising the temperature from room temperature to 300-900 ℃ in nitrogen or argon according to the heating rate of 3-10 ℃/min, and preserving the temperature for 1-5 h;
in the step (4), the acid used in the acidification treatment is dilute H 2 SO 4 Or HCl solution with the concentration of 0.3-0.7M; the acidification treatment time is 3-12 h;
the active atom load of the single-atom catalyst Co is improved to 12-18 wt%.
2. The method for preparing the high-load monoatomic catalyst based on the zeolite imidazole skeleton-67/yeast composite structure according to claim 1, wherein in the step (1), the specific method for activating and culturing the yeast cells is as follows: the mass ratio is 1:1 weighing dry yeast powder and glucose, placing in a beaker, adding deionized water, culturing for 1h under the water bath condition of 37 ℃, and centrifugally washing for 3-5 times to obtain the activated yeast.
3. The method for preparing a high-load single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure according to claim 1, wherein in the step (2), the precursor a has a composite structure of a zeolite imidazole ester skeleton-67 nano-sheets tightly grown on the surface of a yeast cell.
4. The method for preparing a high-loading single-atom catalyst based on a zeolite imidazole ester skeleton-67/yeast composite structure according to claim 1, wherein in the step (3), the precursor B has a regular structure.
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| CN111952570A (en) * | 2020-08-24 | 2020-11-17 | 洛阳理工学院 | Cobalt-nitrogen-carbon composite material containing single-atom active site and preparation method and application thereof |
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| US20210316289A1 (en) * | 2020-04-13 | 2021-10-14 | University Of South Florida | Atomically dispersed metal catalysts and applications thereof |
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| CN111952570A (en) * | 2020-08-24 | 2020-11-17 | 洛阳理工学院 | Cobalt-nitrogen-carbon composite material containing single-atom active site and preparation method and application thereof |
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