CN112593254B - Nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst and preparation method and application thereof - Google Patents

Nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst and preparation method and application thereof Download PDF

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CN112593254B
CN112593254B CN202011364894.4A CN202011364894A CN112593254B CN 112593254 B CN112593254 B CN 112593254B CN 202011364894 A CN202011364894 A CN 202011364894A CN 112593254 B CN112593254 B CN 112593254B
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sulfur
nitrogen
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doped carbon
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CN112593254A (en
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侯阳
李燕
杨彬
雷乐成
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention relates to the technical field of nano materials, and discloses a nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: carrying out hydrothermal reaction on ferric salt, fumaric acid and 1, 2-benzisothiazole-3-ketone to obtain a primary product, filtering and drying the primary product, calcining, pickling and drying the primary product to obtain the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst, wherein iron in the catalyst is anchored in a nitrogen/sulfur co-doped hollow rod-shaped nano carbon structure in a monatomic form, and the atomic ratio of nitrogen to sulfur is 1.8-2.2: 1; h applied to electrocatalytic reduction of oxygen into hydrogen peroxide2O2The selectivity is more than 92%, and the electrochemical performance and stability are excellent.

Description

Nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a nitrogen/sulfur co-doped carbon supported iron monatomic catalyst, and a preparation method and application thereof.
Background
Hydrogen peroxide (H)2O2) As an environment-friendly oxidant and a chemical bleaching agent, the environment-friendly bleaching agent has the excellent characteristics of strong oxidizing property, high efficiency, greenness and no secondary pollution in use, and is widely applied to the fields of chemical industry, papermaking, textile, food, medicine, military, environmental protection and the like. Anthraquinone process for producing H2O2Is one of the most mature production methods in the industry in the world at present, but the catalyst in the anthraquinone method is easy to agglomerate, crush and poison; h produced in the production process2O2The method has the advantages that the method is combined with an organic solvent, the separation difficulty is high, and part of the organic solvent has toxicity, so that the method has certain danger and limits the wide commercial application of the organic solvent. And electrochemical cathode reduction of oxygen to produce H2O2The method has the advantages of high reaction efficiency, safe operation, high current density and the like, and the synthesized H2O2Has the characteristics of no impurities, high purity and the like, and is considered to be the preparation H with the greatest development prospect2O2One of the techniques of (1).
The key to the electrochemical cathodic reduction process is the development of highly selective and active electrocatalysts that are efficient and economically viable. Noble metals and their alloys are currently the most efficient electrocatalysts, but their scarcity prevents their large-scale use. Recent studies have shown that monatomic catalysts have isolated metal atom sites dispersed on a support, and have generally attracted considerable attention for maximum atom utilization, excellent catalytic performance, and a well-defined active center structure. So far, Fe-N-C catalysts dispersed in atomic scale have been reported for many times to be used for electrochemical oxygen reduction and carbon dioxide reduction, and have good performance and good stability, and can be used in the field of electrochemical reduction. For example, Chinese patent publication No. CN111727170A discloses a Fe-N-C catalystThe method prepares a catalytic material containing iron single atoms on an N-doped carbon matrix by pyrolyzing an fe (ii) -doped Zn-Zeolitic Imidazolate Framework (ZIF); the specific method comprises the following steps: (i) dissolving dimethyl imidazole in methanol to obtain a solution A; (ii) by addition of Fe (II) precursors, e.g. FeCl2·4H2O and Zn salts, e.g. Zn (NO)3)2Dissolving in methanol to obtain solution B; (iii) adding the solution B into the solution A, fully reacting and collecting precipitate; (iv) the solid precipitate was placed in a tube furnace for 100mL min-1N of (A)2Pyrolyzing at 900 deg.C for 3 hr at flow rate and at temperature rise rate of 5 deg.C for min-1Obtaining the Fe-N-C catalyst.
For example, Chinese patent publication No. CN111468163A discloses a two-dimensional iron monatomic catalyst, a preparation method thereof and an application thereof in the production of ethylene by reduction of 1, 2-dichloroethane, wherein FeCl is adopted3·6H2The complexation of O with the catechol hydroxyl group of dopamine may affect dopamine polymerization. During the subsequent carbonization process, the layered structure is retained, the final sample morphology is controlled, and when the Fe salt template is removed, two-dimensional carbon nanosheets with the thickness of a few nanometers are generated. Meanwhile, in the carbonization process, carbon layer molecules are rearranged, and Fe element is embedded into the N-doped carbon skeleton structure in a single atom form, so that the two-dimensional iron single-atom catalyst is finally formed.
Despite the progress made, the monoatomic species are used as electrocatalysts for the electrochemical reduction of O2Preparation H2O2Still face the problems of low selectivity, poor stability, etc. Therefore, the electrochemical reduction of O is realized by preparing a nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst2Preparation H2O2Meanwhile, nitrogen/sulfur codoping can further regulate and control the electronic structure of the monatomic iron, so that the electrochemical reduction activity and stability are further improved, and the large-scale preparation of high-concentration H is realized2O2Is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen/sulfur co-doped carbon supported iron atom catalyst with high catalytic activity, high selectivity and good stability, and the method can obtain a hollow coreThe unique structure of the rod-shaped nanometer carbon structure improves the activity and the selectivity of the catalyst and is applied to the electrocatalytic reduction of O2Synthesis of H2O2The electrochemical performance and stability are good.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a nitrogen/sulfur co-doped carbon supported iron monatomic catalyst comprises the following steps: performing hydrothermal reaction on iron salt, fumaric acid and 1, 2-benzisothiazol-3-one to obtain a primary product, filtering and drying the primary product, calcining, pickling and drying the primary product to obtain the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst.
In the invention, fumaric acid is used as an organic ligand, 1, 2-benzisothiazole-3-ketone is used as a regulator to control the growth of a metal organic framework crystal formed by metal Fe and fumaric acid, so that a nanorod-shaped S, N-codoped metal organic framework is formed, the length and width of the metal organic framework are controlled by adding the 1, 2-benzisothiazole-3-ketone, and the S, N ratio is controlled by different calcining temperatures.
The mass ratio of the ferric salt to the fumaric acid to the 1, 2-benzisothiazole-3-ketone is 1-10: 0.1-5: 0.1-2. The iron salt and the fumaric acid can form a rod-shaped metal organic framework within a specified proportion, a nanowire structure can be formed when the proportion of the 1, 2-benzisothiazol-3-one is too high, and a nanoparticle can be formed when the proportion is too low, so that the nanorod structure cannot be formed.
Preferably, the mass ratio of the ferric salt to the fumaric acid to the 1, 2-benzisothiazol-3-one is 1-5: 0.1-0.7: 0.1-0.3. The length and the diameter of the obtained nano rod structure are more uniform only in the proportion.
The iron salt refers to soluble salt of iron, and comprises one of ferric nitrate, ferric chloride, hydrate thereof and the like. Preferably, the iron salt is ferric nitrate hexahydrate or ferric nitrate nonahydrate.
The iron salt, fumaric acid and 1, 2-benzisothiazol-3-one can be dissolved in a solvent, the temperature of the solvent in the dissolving process is 50-80 ℃, and the preferred solvent is water.
The hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 5-24 h. The metal organic framework cannot be formed when the temperature is too low, and the metal organic framework formed violently when the temperature is too high is not uniform.
Preferably, the temperature of the hydrothermal reaction is 100-150 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃. The rod-shaped metal organic framework structure with uniform appearance can be formed in the temperature range. Preferably, the hydrothermal reaction time is 5-10 h.
The calcination temperature is 650-750 ℃, and the calcination time is 1-6 h. Providing a sulfur source and a nitrogen source by using 1, 2-benzisothiazole-3-ketone in the calcining process, adjusting the proportion of nitrogen atoms and sulfur atoms in the catalyst by controlling the calcining temperature so as to obtain the optimal nitrogen-sulfur ratio, wherein the higher the temperature is, the lower the nitrogen content is, the higher the sulfur content is, and when the nitrogen-sulfur atom ratio is about 2:1, the catalyst catalyzes and prepares H2O2The selectivity is highest, and the catalytic effect is optimal.
Preferably, the calcination temperature is 680-730 ℃, such as 680 ℃, 685 ℃, 690 ℃, 700 ℃, 720 ℃ and the like. Too low a temperature easily results in too high a nitrogen-sulfur ratio, and too high a temperature results in too low a nitrogen-sulfur ratio, resulting in a decrease in catalytic activity.
Preferably, the calcination time is 2-4 h.
The acid cleaning is carried out by adopting acid solution etching, the acid solution is hydrochloric acid or sulfuric acid, the molar concentration is 0.1-12M, and the etching time is 2-48 h.
Preferably, the acidic solution is a hydrochloric acid solution, the concentration is 6M, and the etching time is 24 h.
The invention also provides a nitrogen/sulfur co-doped carbon supported iron monatomic catalyst obtained by the preparation method, wherein iron in the catalyst is anchored in a nitrogen/sulfur co-doped hollow rod-shaped carbon nano-structure in a monatomic form, and the atomic ratio of nitrogen to sulfur is 1.8-2.2: 1.
The invention also provides application of the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst in electrocatalytic oxygen reduction to hydrogen peroxide, and the catalyst has excellent electrochemical performance and stability and can be used as a cathode material to be electrically chargedCatalytic production of H2O2Its initial potential is 0.75V, H2O2The selectivity is more than 92 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst has a hollow rod-shaped structure with uniform size and proper sulfur-nitrogen ratio, so the catalyst has excellent catalytic activity and is used for electrocatalytic reduction of O2Synthesis of H2O2The material has good electrochemical performance and stability.
(2) The catalyst has the advantages of simple and efficient preparation method, low cost, high controllability and good reproducibility, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the catalyst prepared in example 1.
FIG. 2 is a transmission electron micrograph of the catalyst prepared in example 1.
FIG. 3 is a high angle annular dark field scanning transmission electron micrograph of the catalyst prepared in example 1.
FIG. 4 shows the electrocatalytic reduction of O in the catalysts prepared in examples 1-3 and comparative example 12Preparation H2O2Curve (c) of (d).
Fig. 5 is a stability test chart of the catalyst prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available, and the molar ratio of nitrogen to sulfur in the obtained catalyst was estimated by testing using X-ray photoelectron spectroscopy.
Example 1
(1) 1.050g of iron nitrate nonahydrate, 0.278g of fumaric acid and 0.196g of 1, 2-benzisothiazol-3-one were added in this order and dissolved in 50mL of a 70 ℃ deionized water solution, and sufficiently stirred for 30 min; transferring the obtained mixed solution into a 100mL hydrothermal kettle, carrying out hydrothermal reaction for 6h at 110 ℃, filtering and drying the obtained sample to obtain an initial product, and doping the nano rod-shaped sulfur into a metal organic framework;
(2) carrying out vacuum tube sealing on the primary product obtained in the step (1), then putting the primary product into a tube furnace, and calcining the primary product at the high temperature of 700 ℃ for 2h, wherein the heating rate is 2 ℃ for min-1(ii) a And (3) etching the sample for 24 hours by adopting 6M hydrochloric acid after calcining, washing the sample to be neutral by using deionized water, and drying the sample to obtain the nitrogen/sulfur co-doped carbon supported iron monatomic catalyst.
The surface morphology of the obtained catalyst was observed by scanning electron microscopy and transmission electron microscopy, and the results are shown in fig. 1 and 2. It can be seen from the figure that the catalyst presents a hollow rod-shaped structure, and the length and the diameter of the rod-shaped structure are uniform and do not agglomerate.
FIG. 3 is a high-angle annular dark field scanning transmission electron microscope image of the catalyst, and clearly shows that iron is uniformly dispersed on the hollow rod-shaped carbon carrier in a monoatomic form.
Example 2
The catalyst was obtained by following the preparation process of example 1 while changing the calcination temperature in step (2) to 600 ℃.
Example 3
The catalyst was obtained by following the preparation process of example 1 while changing the calcination temperature in step (2) to 800 ℃.
Comparative example 1
According to the preparation process of example 1, the catalyst was obtained without adding 1, 2-benzisothiazol-3-one in the step (1) and without changing other conditions.
Application of catalysts for electrochemical reduction of O2Synthesis of H2O2
The method comprises the following specific steps: first, a dispersion liquid having a volume ratio of water/ethanol/Nafion of 4:6:1 was prepared, and then 6uL of the dispersion liquid containing the catalyst materials prepared in examples 1 to 3 and comparative example 1 was respectively dropped on a rotating disk electrode, and after natural drying treatment, it was used as a working electrode. The counter electrode is a platinum column, the reference electrode is a saturated silver/silver chloride electrode, and the electrolyte is 0.1M KOH solution;
cyclic Voltammetric (CV) activation: using electrochemical workstation of CHI 660E, introducing O into electrolyte before testing2Keeping the test time for 0.5h, adopting a CV program, and testing the test interval at 0-1.2V vs. RHE with the sweep rate of 50mV s-1And circularly scanning for 40 circles, and enabling the electrode to reach a stable state.
Linear Sweep Voltammetry (LSV) test: after CV activation, switching the program to an LSV program, wherein the test interval is 0-1.2V vs. RHE, and the sweep rate is 50mV s-1。
The results are shown in FIG. 4, where the catalysts prepared in the examples were paired with electrocatalytic O2Reduction preparation of H2O2The reactivity of (2) is excellent. The catalyst of example 1 had an initial potential of 0.75V, H2O2Selectivity is>92% and has excellent stability, as shown in fig. 5, fig. 5 is the catalytic stability test result of the catalyst of example 1, and it can be seen that the current density stability is unchanged for 10h, which indicates that the electrochemical stability of the catalyst is stable.
The catalyst of example 2 had an initial potential of 0.70V, H2O2The selectivity is 25 percent; the catalyst of example 3 had an initial potential of 0.82V, H2O2The selectivity is 38%; the catalyst of comparative example 1 had an initial potential of 0.82V, H2O2The selectivity was 42%.
The contents of the respective elements in the catalysts obtained in examples 1 to 3 and comparative example 1 were measured by XPS, and the results are shown in Table 1, and the catalyst prepared in example 1 had good H2O2High selectivity, and lower H in examples 2 and 32O2Selectivity, which is due to the low or high nitrogen-sulfur ratio resulting from its calcination temperature, resulting in a decrease in catalytic activity.
Table 1 contents of respective elements in catalysts of examples 1 to 3 and comparative example 1
The content of elements% Example 1 Example 2 Example 3 Comparative example 1
C1s 92.73 88.18 93.73 92.85
O1s 3.8 7.11 3.36 6.6
N1s 1.92 3.09 1.65 0
Fe2p 0.56 0.77 0.41 0.55
S2p 0.99 0.86 1.04 0
N:S[1] 1.94:1 3.6:1 1.59:1 —

Claims (6)

1. A preparation method of a nitrogen/sulfur co-doped carbon supported iron monatomic catalyst is characterized by comprising the following steps: carrying out hydrothermal reaction on ferric salt, fumaric acid and 1, 2-benzisothiazol-3-one to obtain a primary product, filtering and drying the primary product, and then calcining, pickling and drying the primary product to obtain the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst;
the mass ratio of the ferric salt to the fumaric acid to the 1, 2-benzisothiazole-3-ketone is 1-10: 0.1-5: 0.1-2; the hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 5-24 h; the calcining temperature is 650-750 ℃, and the calcining time is 1-6 h.
2. The preparation method of the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst according to claim 1, wherein the mass ratio of the iron salt, the fumaric acid, and the 1, 2-benzisothiazol-3-one is 1-5: 0.1-0.7: 0.1-0.3.
3. The preparation method of the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst according to claim 1, wherein the hydrothermal reaction temperature is 100-150 ℃.
4. The preparation method of the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst according to claim 1, wherein the acid washing is performed by etching with an acidic solution, the acidic solution is hydrochloric acid or sulfuric acid, the molar concentration is 0.1-12M, and the etching time is 2-48 hours.
5. The nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst obtained by the preparation method according to any one of claims 1 to 4, wherein iron in the catalyst is anchored in a nitrogen/sulfur co-doped hollow rod-like carbon nanomaterial in a monatomic form, and the atomic ratio of nitrogen to sulfur is 1.8-2.2: 1.
6. The use of the nitrogen/sulfur co-doped carbon-supported iron monatomic catalyst of claim 5 in electrocatalytic oxygen reduction to hydrogen peroxide.
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