CN116145184A - Preparation method and application of graphene-based composite binary metal sulfide electrocatalyst - Google Patents

Preparation method and application of graphene-based composite binary metal sulfide electrocatalyst Download PDF

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CN116145184A
CN116145184A CN202310036860.XA CN202310036860A CN116145184A CN 116145184 A CN116145184 A CN 116145184A CN 202310036860 A CN202310036860 A CN 202310036860A CN 116145184 A CN116145184 A CN 116145184A
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graphene
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metal sulfide
electrocatalyst
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毕惠婷
朱登霞
王超龙
朱君江
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Wuhan Textile University
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
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    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract

The invention relates to the technical field of electrocatalysis, in particular to a preparation method and application of a graphene-based composite binary metal sulfide electrocatalyst. Graphene is used as a matrix for preparation reaction, and the nano-sheet in-situ growth and metal vulcanization reaction are realized by a hydrothermal one-step method, so that the composite electrocatalyst is prepared. By regulating and controlling the doping amount of Fe element, the nano structure of the composite catalyst can be effectively improved, and MoS can be increased 2 The catalytic activity and the reaction site of the electrocatalyst can also maintain the stability of the catalyst for catalyzing hydrogen evolution reaction for a long time. The method can be used for effectivelyThe problems of low catalytic activity and poor kinetic rate of the single-component catalyst in the water electrolysis reaction process are solved; by graphene recombination, the conductivity of the catalyst is improved and the stability of the catalytic process is increased. The method is simple and feasible, is economical and environment-friendly, can be used for large-scale production and can be applied to the preparation of other metal sulfide electrocatalysts, and the application of electrolyzed water is realized.

Description

Preparation method and application of graphene-based composite binary metal sulfide electrocatalyst
Technical Field
The invention belongs to the technical field of electrocatalysis, and in particular relates to a preparation method and application of a graphene-based composite binary metal sulfide electrocatalyst, wherein graphene is used as a reaction base material, and nano-sheet in-situ growth and metal vulcanization reaction are realized through a hydrothermal one-step method, so that the composite electrocatalyst is prepared.
Background
In order to cope with the impact of energy and environmental crisis and reduce the use of fossil energy, a great deal of exploratory work is carried out on the application of clean energy in China in recent years. The hydrogen energy is used as an energy carrier with energy density larger than that of petroleum, has the most development prospect, is widely available and low in cost, can realize zero carbon emission in the consumption process, and is an ideal primary energy substitute at the present stage. The industrial hydrogen production method is a lot, wherein the electrolytic water hydrogen production takes water as raw material, the process is clean and has no pollutant, and the product has higher purity, thus being one of the most effective hydrogen production modes. In the water electrolysis process, the voltage required by the electrolysis process is increased due to the existence of the overpotential, and the energy consumption is greatly increased, so that the exploration of the electrocatalyst capable of reducing the overpotential and high-efficiency and stability becomes necessary.
Compared with the conventional noble metal electrocatalyst, the two-dimensional metal sulfide has a unique electronic structure, good multi-doping coexistence and excellent material characteristics, and is considered to be a very promising electrocatalyst. However, in the electrocatalytic hydrogen evolution reaction, the metal sulfide has good reactivity, but has poor stability due to the defects of poor conductivity and easy agglomeration, so that the further practical application of the metal sulfide is limited. By increasing the active sites of the metal sulfide, the conductivity of the material is enhanced and the stability of the material is further improved, so that the material is an effective means for improving the catalytic property of the metal sulfide.
Disclosure of Invention
The invention relates to a preparation method and application of a graphene-based composite binary metal sulfide electrocatalyst. The method takes thin graphene as a reaction matrix, realizes in-situ growth of nano sheets and metal vulcanization reaction by a hydrothermal one-step method, and prepares the graphene-based composite binary metal sulfide electrocatalyst named rGO@FeS 2 MoS 2 . The catalyst has the advantages of high activity, good stability, low cost and the like, and has good application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a graphene-based composite binary metal sulfide electrocatalyst comprises the following steps:
adding ferrous chloride, ammonium heptamolybdate and a thin-layer graphene sheet into deionized water, and uniformly dispersing by ultrasonic waves (preferably, carrying out ultrasonic treatment for 3 hours) to obtain a solution A; stirring thiourea to dissolve in glycerol to obtain a solution B; and then placing the solution A to be layered, taking the upper-layer attached graphene (preferably for 3 hours), uniformly mixing the upper-layer attached graphene and the solution B, placing the mixture in a high-pressure reaction kettle, sealing, performing hydrothermal reaction at 180-260 ℃ for 10-30 hours (preferably at 220 ℃ for 18 hours), naturally cooling to room temperature after the reaction is completed, centrifuging the obtained solid, washing (preferably sequentially washing with absolute ethyl alcohol and water), filtering, and vacuum drying to obtain the graphene-based composite binary metal sulfide electrocatalyst.
According to the invention, the metal salt and the graphene are ultrasonically dispersed into the deionized water to form the solution A, so that the metal ions can be uniformly adsorbed on the surface of the graphene, agglomeration of subsequent reaction nano-sheets can be effectively avoided, and uniform in-situ growth and uniform control of morphology of nano-sheets on two sides of the graphene are realized.
By dissolving thiourea in glycerol in the solution B, the glycerol can effectively increase the defects of the nano-sheet layer and increase the catalytic reaction active sites.
Preferably, the vacuum drying conditions are vacuum drying at 60 ℃ for 12 hours.
Preferably, the thin-layer graphene sheet is: graphene sheets with thin-layer structures are obtained after the graphene oxide powder prepared by the traditional hummers method is subjected to ultrasonic and aging treatment;
the conventional hummers method is described with reference to the following documents: hummers, w.s.; offeman, R.E. preparation of graphic oxide.J.am.chem.Soc.1958,80,1339-1339.
More preferably, the steps of ultrasonic and aging treatment are as follows: and (3) after uniformly dispersing graphene oxide powder by ultrasonic waves, standing for overnight for aging, and drying the solid obtained after centrifuging the supernatant at 40 ℃.
Preferably, the molar ratio of the ferrous chloride to the ammonium heptamolybdate is (1-4): 1.
preferably, the dosage ratio of the ferrous chloride, the thin-layer graphene oxide sheets and the thiourea is (0.25-1) mmol:0.1g: (0.1-1.0 g).
The invention also provides application of the catalyst obtained by the preparation method in hydrogen evolution of electrolyzed water.
The preparation method utilizes the means of binary metal co-doping and graphene carbon material compounding to realize the preparation of the graphene composite binary metal sulfide electrocatalyst with high efficiency and stability, avoids particle agglomeration caused by high-temperature sintering, effectively improves the electron transfer capability of the two-dimensional metal sulfide, further enhances the catalytic reaction activity and stability of the two-dimensional metal sulfide, and has good application prospect.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) By regulating and controlling the doping amount of Fe element, the nano structure of the composite catalyst can be effectively improved, and MoS can be increased 2 The catalytic activity and the reaction site of the electrocatalyst can also maintain the stability of the catalyst for catalyzing hydrogen evolution reaction for a long time.
(2) The graphene has a controllable two-dimensional structure and good conductivity, not only can provide metal coordination sites, but also can realize uniform in-situ generation of two-dimensional metal sulfides, and can effectively avoid agglomeration of an active catalyst; and graphene as an interlayer material can provide a lower charge transfer resistance for the catalyst and further increase the HER activity of the catalyst.
(3) The method is simple and feasible, is economical and environment-friendly, can be produced in large scale and applied to the preparation of other metal sulfide electrocatalysts such as Ni, co and the like, and can be applied to the electrolysis of water.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the catalyst obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the catalyst obtained in example 1;
FIG. 3 is an electrode polarization curve of the catalysts obtained in examples 1-3 and comparative examples in an electrolyte;
FIG. 4 shows Tafel slopes corresponding to electrode polarization curves for catalysts obtained in examples 1-3 and comparative examples;
fig. 5 is a TEM image of the graphene oxide sheet having a thin layer structure obtained in example 1.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The following examples were conducted using a conventional hummers method for preparing graphene oxide, with reference to the following references: hummers, w.s.; offeman, R.E. preparation of graphic oxide.J.am.chem.Soc.1958,80,1339-1339.
The glycerol used in the examples below is anhydrous glycerol;
the concentration of the concentrated sulfuric acid and the concentration of the hydrochloric acid are both in mass percent.
Example 1: a preparation method of a graphene-based composite binary metal sulfide electrocatalyst comprises the following steps:
(1) Graphene oxide is prepared by a traditional hummers method and is subjected to primary centrifugal drying: under the ice water bath condition, a 250mL reaction bottle is assembled, 10mL of concentrated sulfuric acid with the concentration of 95% is added into the reaction bottle, 2g of graphite powder and 1g of solid mixture of sodium nitrate are added into the reaction bottle under stirring, 6g of potassium permanganate is added into the reaction bottle for 3 times, the reaction temperature is controlled to be not more than 20 ℃, the reaction bottle is stirred for 30min, then the reaction bottle is heated to about 35 ℃, stirring is continued for 30min, 100mL of deionized water is slowly added into the reaction bottle, stirring is continued for 20min, and 2mL of hydrogen peroxide is added into the reaction bottle to reduce residual oxidant, so that the solution turns into bright yellow. Filtered while hot and washed with 5% hc1 solution and deionized water until no sulfate was detected in the filtrate. And finally, placing the filter cake in a vacuum drying oven at 60 ℃ to fully dry to obtain graphite oxide powder, and preserving for later use.
Dispersing the obtained graphite oxide powder into deionized water, carrying out ultrasonic treatment at a power of 60W for 3 hours, precipitating overnight, taking the solid after supernatant centrifugation, putting the solid into an oven, and drying at 40 ℃ for 3 hours to obtain a graphene oxide sheet with a thin layer structure for later use, wherein a TEM image is shown in FIG. 5;
(2) Adding 0.25mmol of ferrous chloride, 0.25mmol of ammonium heptamolybdate and 0.1g of thin-layer graphene oxide sheet prepared in the step (1) into 30mL of deionized water, and performing ultrasonic dispersion for 3 hours at 60W to obtain a solution A (the step enables metal ions to be uniformly adsorbed on the surface of graphene at first, can effectively avoid agglomeration of nano sheets in subsequent reaction, and realizes uniform in-situ growth and uniform morphology control of nano sheets on two sides of graphene), and stirring and dissolving 0.571g of thiourea into 5mL of glycerin to obtain a solution B (the thiourea is dissolved in the glycerin, the glycerin can effectively increase defects of nano sheets and catalytic reaction sites). Placing the solution A for 3 hours, taking the graphene attached to the upper layer, mixing the graphene with the solution B, stirring the mixture for 30 minutes under ultrasonic treatment to ensure uniform dispersion of raw materials, transferring the solution obtained by uniformly mixing into a 50mL high-pressure reaction kettle, sealing, carrying out hydrothermal reaction for 18 hours at 220 ℃ (the hydrothermal reaction can realize metal vulcanization and graphene reduction), naturally cooling to room temperature, centrifuging, washing the obtained solid with absolute ethyl alcohol and water for 4 times in sequence, and vacuum drying the washed solid at 60 ℃ for 12 hours to obtain the product, namely the high-efficiency stable graphene-based composite binary metal sulfide electrocatalyst.
Example 2: an efficient stable graphene-based composite binary metal sulfide electrocatalyst was prepared according to the method of example 1, except that: the dosage of ferrous chloride is changed to 0.5mmol, and the types and the dosage of other raw materials are unchanged, and the reaction conditions and parameters are unchanged.
Example 3: an efficient stable graphene-based composite binary metal sulfide electrocatalyst was prepared according to the method of example 1, except that: the dosage of ferrous chloride is changed to 1mmol, and the types and the dosage of other raw materials are unchanged, and the reaction conditions and parameters are unchanged.
Comparative example: 0.5mmol of ferrous chloride and 0.25mmol of ammonium heptamolybdate were added to 30mL of deionized water, dispersed ultrasonically for 3 hours, designated solution A, while 0.571g of thiourea was dissolved in 5mL of glycerol with stirring, designated solution B. After the solution A is placed for 3 hours, the solution A is mixed with the solution B, stirred for 30 minutes under ultrasound to ensure that the raw materials are uniformly dispersed, the mixed solution is transferred into a 50mL high-pressure reaction kettle, and the mixture is subjected to hydrothermal treatment at 220 ℃ for 18 hours after being sealed. And naturally cooling to room temperature after the completion, centrifuging to obtain a solid, washing the solid with ethanol and water for 4 times in sequence, and vacuum drying the centrifuged solid at 60 ℃ for 12 hours to obtain the product composite binary metal sulfide electrocatalyst.
FIG. 1 is an XRD spectrum of the catalyst obtained in example 1, showing that: the catalyst obtained is prepared from FeS 2 (PDF 74-1051) and MoS 2 (PDF 86-2308) composition, while proving FeS 2 Is introduced without changing MoS 2 Is a structural feature of (a).
FIG. 2 is a scanning electron microscope image of the catalyst obtained in example 1, as can be seen from the figure: the metal sulfide nano-sheets with uniform structures in the obtained electrocatalyst uniformly grow on two sides of the electrocatalyst by taking the thin-layer graphene as a template, and an interlayer sandwich structure is displayed. This structure can provide a large number of active sites, and can greatly promote catalytic activity and efficiency. Meanwhile, the metal sulfide nano-sheets and the surface chemical bonds of the graphene are subjected to cross-linking interaction, so that the electron transfer resistance in the catalytic process is effectively reduced, and the process stability is enhanced.
Electrolytic hydrogen evolution activity and stability test:
the catalyst prepared in example 1 was subjected to an electrolytic hydrogen evolution test: a three-electrode test system is adopted on an electrochemical workstation, wherein a working electrode is a catalyst electrode (4 mg of the catalyst obtained in the example 1 is dispersed in 1mL of a mixed solution of absolute ethyl alcohol and nafion solution with the volume ratio of 95:5, 14 mu L of the obtained dispersion is uniformly dripped on a glassy carbon electrode to prepare the catalyst electrode), a counter electrode is a graphite electrode, and a reference electrode is an Ag/AgCl (3.5M KCl) electrode. The test electrolyte is a potassium hydroxide aqueous solution with the temperature of 25 ℃ and the concentration of 1mmol/L, high-purity nitrogen is introduced into the test to carry out saturation treatment, and the test temperature is room temperature. The scanning rate was 5mV/s for the linear sweep voltammogram test.
The other catalysts and comparative examples were tested in the manner described above.
FIG. 3 shows the electrode polarization curves of the products obtained in examples 1-3 in the electrolyte, from which the catalysts obtained in examples 1-3 were shown to be at 10mA cm -2 The overpotential is 163mV, 93mV and 166mV respectively, and shows good HER activity, while the overpotential is 300mV in the comparative example under the same current density because of uncomplexed graphene, which shows that the graphene plays an important role in improving the activity of the catalyst.
FIG. 4 shows the Tafel slope corresponding to the electrode polarization curve of the product obtained in examples, wherein the Tafel slope of the catalysts obtained in examples 1-3 is 70.250mV × dec -1 、50mV﹒dec -1 、79.150mV﹒dec -1 It can be seen that the HER kinetic performance of the electrocatalyst can be effectively enhanced through doping proportion regulation and control. The Tafel slope of the comparative example was 71.30 mV. Dec -1 The graphene is shown to be capable of effectively enhancing the dynamic performance of the metal sulfide.
The preparation method utilizes the means of binary metal co-doping and graphene carbon material compounding to realize the preparation of the graphene composite binary metal sulfide electrocatalyst with high efficiency and stability, avoids particle agglomeration caused by high-temperature sintering, effectively improves the electron transfer capability of the two-dimensional metal sulfide, further enhances the catalytic reaction activity and stability of the two-dimensional metal sulfide, and has good application prospect.
It should be noted that modifications or variations can be made by persons skilled in the art in light of the above description, and such modifications or variations are intended to be included within the scope of the appended claims.

Claims (7)

1. A preparation method of a graphene-based composite binary metal sulfide electrocatalyst comprises the following steps:
adding ferrous chloride, ammonium heptamolybdate and a thin-layer graphene sheet into deionized water, and uniformly dispersing by ultrasonic to obtain a solution A; stirring thiourea to dissolve in glycerol to obtain a solution B; and then placing the solution A to be layered, taking the graphene attached to the upper layer, uniformly mixing the graphene attached to the upper layer with the solution B, placing the mixture into a high-pressure reaction kettle, sealing, carrying out hydrothermal reaction at 180-260 ℃ for 10-30h, naturally cooling to room temperature after the reaction is completed, centrifuging the obtained solid, washing, filtering, and vacuum drying to obtain the graphene-based composite binary metal sulfide electrocatalyst.
2. The method according to claim 1, wherein the vacuum drying condition is vacuum drying at 60 ℃ for 12 hours.
3. The method of claim 1, wherein the thin graphene sheets are: graphene oxide powder prepared by the traditional hummers method is subjected to ultrasonic and aging treatment to obtain the graphene sheet with the thin-layer structure.
4. A method of manufacture according to claim 3, wherein the step of ultrasound and aging treatment comprises: and (3) after uniformly dispersing graphene oxide powder by ultrasonic waves, standing for overnight for aging, and drying the solid obtained after centrifuging the supernatant at 40 ℃.
5. The preparation method according to claim 1, wherein the molar ratio of ferrous chloride to ammonium heptamolybdate is (1-4): 1.
6. the preparation method of claim 5, wherein the dosage ratio of the ferrous chloride, the thin graphene oxide sheets and the thiourea is (0.25-1) mmol:0.1g: (0.1 to 1.0 g).
7. Use of the catalyst obtained by the preparation method of any one of claims 1 to 6 in hydrogen evolution of electrolyzed water.
CN202310036860.XA 2022-10-28 2023-01-10 Preparation method and application of graphene-based composite binary metal sulfide electrocatalyst Pending CN116145184A (en)

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