CN116581307B - S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof - Google Patents

S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof Download PDF

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CN116581307B
CN116581307B CN202310727653.9A CN202310727653A CN116581307B CN 116581307 B CN116581307 B CN 116581307B CN 202310727653 A CN202310727653 A CN 202310727653A CN 116581307 B CN116581307 B CN 116581307B
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zif
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methylimidazole
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崔立峰
高鑫
高维康
陈佳怡
甄正
张新河
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Guangdong Green Saifu Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
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Abstract

The invention relates to an S-doped NC/Co/Cs 2 A process for preparing a Se/CoSe catalyst comprising: 1) Preparing 2-methylimidazole microemulsion; 2) The 2-methylimidazole microemulsion, cobalt salt and cesium salt are subjected to coordination reaction to generate Cs x Co 1‑x -ZIF; 3) Causing the Cs to x Co 1‑x The ZIF and the etchant are subjected to etching reaction to generate modified Cs x Co 1‑x -ZIF; 4) Under nitrogen atmosphere, modified Cs x Co 1‑x The ZIF reacts with the selenium powder to obtain S doped NC/Co/Cs 2 Se/CoSe catalysts. The S-doped NC/Co/Cs prepared by the preparation method 2 Se/CoSe catalysts. The S doped NC/Co/Cs 2 Use of Se/CoSe catalysts in fuel cells. The invention has the advantages of low preparation cost, high conductivity and electrocatalytic activity, excellent stability and long service life.

Description

S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials of fuel cells, in particular to an S-doped NC/Co/Cs 2 Se/CoSe catalyst, its preparation method and application.
Background
The catalyst is an important component for realizing high-efficiency conversion of hydrogen energy by the PEMFC. At present, pt/C is the most widely used catalyst material on the market, but noble metal catalyst material has high cost and poor durability under the operation condition of PEMFC, and Pt-based electrocatalyst is easy to generate carbon monoxide poisoning so as to reduce activity, which becomes a main challenge for large-scale commercialization of PEMFC. To address such problems, many Pt-based metal free catalysts have been developed heretofore, such as oxides, sulfides and selenides. Among them, metal selenides, because of their high bulk density and small band gap, exhibit higher bulk capacity and rate performance than oxides or sulfides, and are considered as catalyst materials with good application prospects. The Zeolite Imidazole Skeleton (ZIFs) is easily converted into a nitrogen-doped carbon material through direct carbonization, has higher electronic conductivity and more active sites, and can synthesize the porous metal selenide with high conductivity, so that the inherent characteristics of the selenide are changed.
Heteroatom doping is an effective way to further optimize Co-based electrocatalyst activity. P-doped CoSe is reported 2 In the ORR and OER processes, the local electron density is increased and the free energy is reduced, thereby significantly improving the electrocatalytic properties. S-doped electrocatalysts have also attracted much attention, where it is thought that S-doping increases reactivity due to several aspects: (1) The doping of S atoms reduces the band gap of the catalyst, improves the conductivity of the catalyst, and is beneficial to electrocatalytic oxygen reduction reaction; (2) The doping of S atoms can improve the oxygen adsorption capacity of the catalyst, and is beneficial to oxygen reduction reaction; (3) The introduction of four S atoms into the system can reduce the overpotential of the oxygen reduction reaction and improve the activity of catalyzing the oxygen reduction reaction by the metal site.
Recently, heterojunction structures widely used for photocatalysts have also been employed and have proven useful in many Co-based electrocatalysts, including CoO/CoS, co 2 P/CoP and CoP/CoOOH. In particular, when a conductive zero-valent metal is in close contact with a semiconductor metal compound, a rectifying schottky junction or a non-rectifying ohmic junction will be formed due to the difference in fermi level, which is referred to as the mott-schottky effect. This effect results in built-in electric fields and spontaneous electron flow within the metal-semiconductor heterojunction, which more effectively adjusts the electron structure than the semiconductor-semiconductor heterojunction.
Therefore, the development of an S-doped Mort-Schottky ZIF electrocatalyst has important significance.
Disclosure of Invention
Based on the above, it is necessary to provide an S-doped NC/Co/Cs for solving the problems of high cost, poor durability and poor dispersibility of the existing catalyst 2 Se/CoSe catalyst, its preparation method and application.
S-doped NC/Co/Cs 2 The preparation method of the Se/CoSe catalyst comprises the following steps:
1) Preparing 2-methylimidazole microemulsion;
2) Subjecting the 2-methylimidazole microemulsion, cobalt salt and cesium salt to a complexation reaction to form Cs x Co 1-x -ZIF；
3) Causing the Cs to x Co 1-x -the ZIF undergoes an etching reaction with an etchant to produce modified Cs x Co 1-x -ZIF；
4) Under nitrogen atmosphere, subjecting the modified Cs x Co 1-x The ZIF reacts with the selenium powder to obtain S doped NC/Co/Cs 2 Se/CoSe catalysts.
In step 3) Cs is etched by an etchant x Co 1-x -ZIF surface building defects to adjust the electronic structure of the catalyst to increase the activity of the reaction.
As a preferred embodiment, the step of preparing the 2-methylimidazole microemulsion comprises:
a) Uniformly dispersing 2-methylimidazole in a first solvent to obtain a dispersed phase;
b) The disperse phase and the continuous phase oil form 2-methylimidazole microemulsion under the emulsification action of an emulsifier and a coemulsifier.
As a preferred embodiment, the Cs x Co 1-x The value of x in ZIF is 0<x<1。
As a preferable mode, the concentration of the 2-methylimidazole in the disperse phase is 0.1-0.5 mol/L.
As a more preferable mode, the concentration of the 2-methylimidazole in the dispersed phase is 0.3 to 0.5mol/L.
As a preferred embodiment, the first solvent is deionized water or acetone.
As a preferable scheme, the continuous oil phase is one of white oil, kerosene and diesel oil.
As a preferable scheme, the emulsifier is a compound of Span-series emulsifier and Tween-series emulsifier, or a compound of Span-series emulsifier and OP-series emulsifier.
As a preferred embodiment, the Span-series emulsifying agent is one or more of Span-85, span-80, span-65, span-60, span-40 and Span-20.
As a preferred scheme, the Tween series emulsifying agent is one or more of Tween-20, tween-40, tween-60 and Tween-80.
As a preferred embodiment, one or more of the OP-series emulsifiers OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40 and OP-50.
As a preferable mode, the mass ratio of the Span series emulsifier to the Tween series emulsifier is (2-6): 1.
As a preferable mode, the mass ratio of the Span-series emulsifier to the OP-series emulsifier is (2-6): 1.
As a preferred scheme, the co-emulsifier is one of n-butanol, propylene glycol and isopropanol.
As a preferable mode, the volume ratio of the dispersed phase to the continuous oil phase is (1-8): 20.
as a more preferable mode, the volume ratio of the dispersed phase to the continuous oil phase is (3-5): 20.
as a preferable scheme, the mass of the emulsifier is 3-5 w/v% of the volume of the continuous oil phase.
As a preferable scheme, the volume ratio of the auxiliary emulsifier to the continuous oil phase is (0.5-0.1): 1.
as a preferable scheme, the disperse phase, the continuous oil phase, the emulsifier and the auxiliary emulsifier are stirred for 30-60 min under the conditions that the temperature is 25-35 ℃ and the stirring speed is 600-800 r/min, so as to obtain the 2-methylimidazole microemulsion.
As a preferred embodiment, the cobalt salt is cobalt nitrate or cobalt sulfate.
As a preferable scheme, the molar ratio of the cobalt salt to the 2-methylimidazole is (2-5): 25.
as a preferred embodiment, the cesium salt is cesium nitrate, cesium sulfate or cesium chloride.
As a preferable scheme, the molar ratio of the cobalt salt to the 2-methylimidazole is (1-3): 25.
as a preferable scheme, the reaction temperature of the coordination reaction of the 2-methylimidazole microemulsion, cobalt salt and cesium salt is 25-35 ℃.
As a preferable scheme, the 2-methylimidazole microemulsion, cobalt salt and cesium salt are uniformly mixed by stirring.
Preferably, the stirring mode is magnetic stirring or mechanical stirring.
As a preferable mode, the stirring speed is 600-800 r/min.
As a preferable mode, the stirring time is 60-90 min.
As a preferable scheme, after the coordination reaction of the 2-methylimidazole microemulsion, cobalt salt and cesium salt is finished, the Cs is obtained after ethanol demulsification, centrifugation and freeze drying x Co 1-x -ZIF。
As a preferable scheme, the rotation speed of the centrifugation is 10000-15000 r/min.
As a preferable mode, the centrifugation time is 10-20 min.
As a preferable mode, the temperature of the freeze drying is-50 ℃ to-60 ℃.
As a preferable mode, the freeze drying time is 16-24 hours.
Preferably, the pressure of the freeze-drying is 5 to 10Pa.
As a preferred embodiment, the Cs x Co 1-x -the ZIF is etched with an etchant in a second solvent.
As a preferred embodiment, the second solvent is anhydrous methanol or anhydrous ethanol.
As a preferable scheme, the etchant is sulfonated humic acid or sulfonated tannic acid.
The sulfonated humic acid and the sulfonated tannic acid can be adsorbed on the surface of the ZIF material, and on one hand, H is ionized + And etching the ZIF materials, and inhibiting aggregation among the ZIF materials on one hand.
The surfaces of the sulfonated humic acid and the sulfonated tannic acid have rich sulfonated groups (sulfonic groups or sulfonyl chloride groups), and S element can be introduced to the surface of the ZIF material, so that the band gap of the catalyst is reduced to a certain extent, and the conductivity and the stability of the catalyst are improved.
As a preferred embodiment, the Cs x Co 1-x -Cs in solution of ZIF in the second solvent x Co 1-x The concentration of the ZIF is 1-10 g/L.
As a preferred embodiment, the Cs x Co 1-x The mass ratio of the ZIF to the etchant is 1 (5-10).
As a preferable scheme, the reaction temperature of the etching reaction is 35-45 ℃.
As a preferred embodiment, the Cs x Co 1-x The etching reaction of the ZIF with the etchant is carried out during stirring.
Preferably, the stirring mode is magnetic stirring or mechanical stirring.
As a preferable mode, the stirring speed is 600-800 r/min.
As a preferable mode, the stirring time is 5-8 h.
As a preferable scheme, after the etching reaction is finished, the modified Cs is obtained after freeze drying x Co 1-x -ZIF。
In step 4), the modified Cs x Co 1-x 2-methylimidazole, sulfonated humic acid or sulfonated tannic acid in ZIF will be pyrolyzed under high temperature nitrogen atmosphere, and finally S-doped NC is formed. Wherein, the sulfonated humic acid or the sulfonated tannic acid can introduce S element on the surface of the material to form S doped material; and the modified Cs x Co 1-x Cs and Co in the ZIF are selenized with selenium powder respectively to obtain CsSe and CoSe.
As a preferred embodiment, the modified Cs x Co 1-x The mass ratio of the ZIF to the selenium powder is 1 (0.8-3).
As a more preferred embodiment, the modified Cs x Co 1-x The mass ratio of the ZIF to the selenium powder is 1 (1.5-2.5).
As a preferred embodiment, the Cs is modified under a nitrogen atmosphere x Co 1-x Mixing ZIF and selenium powder, placing in a tube furnace, heating to 350deg.C for 3 hr, heating to 900deg.C for 1 hr,finally, heating to 1000 ℃ and keeping for 3 hours to obtain the S-doped NC/Co/Cs 2 Se/CoSe catalysts.
S-doped NC/Co/Cs prepared by the preparation method 2 Se/CoSe catalysts.
As a preferable scheme, the S-doped NC/Co/Cs 2 The average particle size of the Se/CoSe catalyst is 200-800nm.
As a more preferable scheme, the S-doped NC/Co/Cs 2 The average particle size of the Se/CoSe catalyst is 200-400nm.
S-doped NC/Co/Cs as described above 2 Se/CoSe catalysts react in the fuel cell cathode oxygen reduction reaction.
Compared with the prior art, the S-doped NC/Co/Cs provided by the invention 2 The Se/CoSe catalyst has the following beneficial effects:
(1) Compared with a commercial Pt/C electrocatalyst, the S-doped NC/Co/Cs of the invention 2 The Se/CoSe catalyst has low noble metal content, effectively reduces the cost of the catalyst, and is beneficial to the commercialization development of fuel cells.
(2) Compared with the commercial Pt/C electrocatalyst, the catalyst (S doped NC/Co/Cs 2 The Se/CoSe catalyst has excellent conductivity and electrocatalytic activity, and is beneficial to promoting the commercialization development of fuel cells.
(3) Compared with a commercial Pt/C electrocatalyst, the S-doped NC/Co/Cs of the invention 2 The Se/CoSe catalyst has excellent stability and long service life, and is beneficial to the commercialization development of proton exchange membrane fuel cells.
Drawings
FIG. 1 is a sample of the S-doped NC/Co/Cs prepared in example 1 2 SEM image of Se/CoSe catalyst.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
(1) Adding 0.012-methylimidazole into 40mL of deionized water, and stirring at a stirring speed of 600r/min for 30min at a temperature of 25 ℃ to obtain a disperse phase-1;
(2) Adding 4g of span80, 2g of Tween20 and 20mL of n-butanol into 200mL of white oil in sequence, and stirring for 20min at a stirring speed of 600r/min to form light blue water-in-oil microemulsion; then adding 30mL of disperse phase-1, and stirring for 30min at the stirring speed of 600r/min at the temperature of 25 ℃ to obtain 2-methylimidazole microemulsion-1;
(3) Sequentially adding 0.0024mol of cobalt nitrate and 0.00144mol of cesium nitrate into 2-methylimidazole microemulsion-1, stirring at a stirring speed of 600r/min at a temperature of 25 ℃ for 60min, demulsifying with ethanol after the reaction is finished, washing to obtain suspension-1, centrifuging the suspension-1 at a centrifugal speed of 10000r/min for 20min to obtain precipitate-1, and freeze-drying the precipitate-1 at a temperature of-50 ℃ and a drying pressure of 5Pa for 16h to obtain Cs x Co 1-x -ZIF-1；
(4) To 100mL of anhydrous methanol, 1g of Cs was added sequentially x Co 1-x ZIF-1 and 10g of sulfonated tannic acid, heating to 35 ℃, and etching at 600r/min for 5h to obtain modified Cs x Co 1-x -ZIF material-1;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-1 and 25g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-1;
doping NC/Co/Cs with S 2 The Se/CoSe Catalyst-1 was named Catalyst-1 and had an average particle size of 203.35nm.
Example 2
(1) Adding 0.025mol 2-methylimidazole into 50mL of acetone, and stirring at a stirring speed of 800r/min for 60min at a temperature of 35 ℃ to obtain a disperse phase-2;
(2) 7.5g of span60, 2.5g of OP10 and 10mL of propylene glycol are sequentially added into 200mL of kerosene, and stirred for 20min under the condition of stirring speed of 800r/min to form light blue water-in-oil microemulsion; then 50mL of disperse phase-2 is added, and stirring is carried out for 60min at the stirring speed of 800r/min under the condition of the temperature of 35 ℃ to obtain 2-methylimidazole microemulsion-2;
(3) Sequentially adding 0.002mol of cobalt sulfate and 0.001mol of cesium sulfate into 2-methylimidazole microemulsion-2, stirring at a temperature of 35 ℃ for 90min at a stirring speed of 800r/min, demulsifying with ethanol after the reaction is finished, washing to obtain suspension-2, centrifuging the suspension-2 at a centrifugation speed of 15000r/min for 10min to obtain precipitate-2, and freeze-drying the precipitate-2 at a temperature of-60 ℃ under a drying pressure of 10Pa for 24h to obtain Cs x Co 1-x -ZIF-2；
(4) In 100mL of anhydrous methanol, 0.1g of Cs was added sequentially x Co 1-x ZIF-2 and 0.5g of sulfonated humic acid, heating to 45 ℃, and etching at 800r/min for 8h to obtain modified Cs x Co 1-x -ZIF material-2;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-2 and 15g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-2;
doping NC/Co/Cs with S 2 Se/CoSe Catalyst-2 was named Catalyst-2 and had an average particle size of 342.68nm.
Example 3
(1) Adding 0.02mol of 2-methylimidazole into 50mL of deionized water, and stirring at a stirring speed of 700r/min for 45min at a temperature of 30 ℃ to obtain a disperse phase-3;
(2) 6.7g of span85, 1.3g of OP40 and 15mL of isopropanol are sequentially added into 200mL of diesel oil, and stirred for 20min under the condition of stirring speed of 700r/min to form light blue water-in-oil microemulsion; then 40mL of disperse phase-3 is added, and stirring is carried out for 45min at the stirring speed of 700r/min under the condition of 30 ℃ to obtain 2-methylimidazole microemulsion-3;
(3) Sequentially adding 0.002mol of cobalt nitrate and 0.001mol of cesium chloride into 2-methylimidazole microemulsion-3, stirring at a temperature of 30 ℃ for 75min at a stirring speed of 700r/min, demulsifying with ethanol after the reaction is finished, washing to obtain suspension-3, centrifuging the suspension-3 at a centrifugal speed of 12500r/min for 15min to obtain precipitate-3, and freeze-drying the precipitate-3 at a temperature of-55 ℃ and a drying pressure of 8Pa for 20h to obtain Cs x Co 1-x -ZIF-3；
(4) In 100mL of anhydrous methanol, 0.5g of Cs was added sequentially x Co 1-x -ZIF-3 and 3.5g of sulfonated humic acid, heating to 40 ℃, and etching at 700r/min for 6.5h to obtain modified Cs x Co 1-x -ZIF material-3;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-3 and 20g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-3.
Doping NC/Co/Cs with S 2 Se/CoSe Catalyst-3 was named Catalyst-3 and had an average particle size of 284.13nm.
Example 4
(1) Adding 0.005mol of 2-methylimidazole into 50mL of acetone, and stirring at a stirring speed of 650r/min for 40min at a temperature of 25 ℃ to obtain a disperse phase-4;
(2) 5.5g of span25, 1.0g of OP7 and 12mL of propylene glycol are sequentially added into 200mL of white oil, and the mixture is stirred for 20min under the condition of a stirring speed of 650r/min, so that light blue water-in-oil microemulsion is formed; then adding 10mL of disperse phase-4, and stirring for 40min at the stirring speed of 650r/min at the temperature of 28 ℃ to obtain 2-methylimidazole microemulsion-4;
(3) Adding 0.0006mol of cobalt sulfate and 0.0004mol of cesium nitrate into 2-methylimidazole microemulsion-4 in sequence, stirring at the temperature of 28 ℃ for 70min at the stirring speed of 650r/min, and demulsifying by using ethanol after the reaction is finishedWashing to obtain suspension-4, centrifuging at 11000r/min for 12min to obtain precipitate-4, and lyophilizing at-51deg.C under 9Pa for 17 hr to obtain Cs x Co 1-x -ZIF-4；
(4) In 100mL of anhydrous methanol, 0.3g of Cs was added sequentially x Co 1-x -ZIF-4 and 2.7g of sulfonated tannic acid, heating to 37 ℃, and etching at 650r/min for 6h to obtain modified Cs x Co 1-x -ZIF material-4;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-4 and 8g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-4.
Doping NC/Co/Cs with S 2 Se/CoSe Catalyst-4 was named Catalyst-4 and had an average particle size of 448.59nm.
Example 5
(1) Adding 0.01mol of 2-methylimidazole into 50mL of deionized water, and stirring at a stirring speed of 750r/min for 50min at a temperature of 27 ℃ to obtain a disperse phase-5;
(2) 7.5g of span40, 1.5g of Tween40 and 16mL of n-butanol are sequentially added into 200mL of diesel oil, and stirring is carried out for 20min under the condition of a stirring speed of 750r/min, so as to form light blue water-in-oil microemulsion; then 80mL of disperse phase-5 is added, and stirring is carried out for 50min at the stirring speed of 750r/min under the condition of the temperature of 32 ℃ to obtain 2-methylimidazole microemulsion-5;
(3) Sequentially adding 0.0016mol of cobalt nitrate and 0.001mol of cesium sulfate into 2-methylimidazole microemulsion-5, stirring at a stirring speed of 750r/min for 80min at a temperature of 33 ℃, demulsifying by using ethanol after the reaction is finished, washing to obtain suspension-5, centrifuging the suspension-5 at a centrifugal speed of 14000r/min for 18min to obtain precipitate-5, and freeze-drying the precipitate-5 at a temperature of-56 ℃ and a drying pressure of 7Pa for 22h to obtain Cs x Co 1-x -ZIF-5；
(4) In 100mL of anhydrous methanol, 0.8g of Cs was added sequentially x Co 1-x -ZIF-5 and 6.4g sulfoDissolving tannic acid, heating to 42 ℃, and etching for 7h at 750r/min to obtain modified Cs x Co 1-x -ZIF material-5;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-5 and 30g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-5.
Doping NC/Co/Cs with S 2 Se/CoSe Catalyst-5 was named Catalyst-5 and had an average particle size of 612.85nm.
Example 6
(1) Adding 0.0075mol of 2-methylimidazole into 50mL of deionized water, and stirring at a stirring speed of 620r/min for 53min at 34 ℃ to obtain a disperse phase-6;
(2) 7.2g of span80, 1.8g of OP50 and 16mL of isopropanol are sequentially added into 200mL of white oil, and the mixture is stirred for 20min under the condition of a stirring speed of 720r/min to form light blue water-in-oil microemulsion; then adding 20mL of disperse phase-6, and stirring for 40min at a stirring speed of 600r/min at 34 ℃ to obtain 2-methylimidazole microemulsion-6;
(3) Sequentially adding 0.0012mol of cobalt sulfate and 0.0003mol of cesium chloride into 2-methylimidazole microemulsion-6, stirring at a stirring speed of 650r/min for 85min at a temperature of 34 ℃, demulsifying and washing by using ethanol after the reaction is finished to obtain suspension-6, centrifuging the suspension-6 at a centrifugation speed of 15000r/min for 11min to obtain precipitate-6, and freeze-drying the precipitate-6 at a temperature of-52 ℃ and a drying pressure of 5Pa for 19h to obtain Cs x Co 1-x -ZIF-6；
(4) In 100mL of absolute ethanol, 0.6g of Cs are added in sequence x Co 1-x -ZIF-6 and 4.2g of sulfonated tannic acid, heating to 42 ℃, and etching at 700r/min for 8h to obtain modified Cs x Co 1-x -ZIF material-6;
(5) 10g of modified Cs are reacted x Co 1-x Uniformly mixing ZIF-6 and 28g selenium powder, placing in a tube furnace, heating to 350 ℃ under nitrogen atmosphere for 3h, heating to 900 ℃ for 1h, and heating to 1000 ℃ for 3h to obtain S-doped NC/Co/Cs 2 Se/CoSe catalyst-6.
Doping NC/Co/Cs with S 2 Se/CoSe Catalyst-6 was named Catalyst-6 and had an average particle size of 771.39nm.
Comparative example 1
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in the step (1), the amount of 2-methylimidazole added was 0.3mol.
The resulting product was designated D-1 and had an average particle size of 1.58. Mu.m.
Comparative example 2
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (2), "4g span80, 2g Tween20" was not added.
The product obtained was designated D-2 and had an average particle size of 883.95nm.
Comparative example 3
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in the step (2), the addition amount of n-butanol was 60mL.
The resulting product was designated as D-3 and had an average particle diameter of 1.98. Mu.m.
Comparative example 4
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in the step (2), the addition amount of the dispersed phase was 100mL.
The resulting product was designated as D-4 and had an average particle diameter of 1.12. Mu.m.
Comparative example 5
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (3), cesium nitrate is not added.
The product obtained was designated D-5 and had an average particle size of 268.25nm.
Comparative example 6
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (3), cesium nitrate is not added.
The product obtained was designated D-6 and had an average particle size of 268.25nm.
Comparative example 7
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (4), sulfonated tannic acid is not added.
The product obtained was designated D-7 and had an average particle size of 468.25nm.
Comparative example 8
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (4), the "10g of sulfonated tannic acid" is replaced with "10g of acetic acid".
The product obtained was designated D-8 and had an average particle size of 685.44nm.
Comparative example 9
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in step (5), 25g of selenium powder was not added.
The product obtained was designated D-9 and had an average particle size of 314.86nm.
Comparative example 10
Preparation of S-doped NC/Co/Cs in the same manner as in example 1 2 Se/CoSe catalysts are different in that: in the step (5), the temperature is raised to 350 ℃ for 3 hours under the nitrogen atmosphere in the step (5), then is raised to 900 ℃ for 1 hour, and finally is raised to 1000 ℃ for 3 hours, and the temperature is raised to 1000 ℃ for 7 hours.
The product obtained was designated D-10 and had an average particle size of 286.91nm.
Test example 1
The S-doped NC/Co/Cs prepared in example 1 was examined using an SEM scanning electron microscope 2 The Se/CoSe catalyst was tested and the test results are shown in FIG. 1.
Test example 2
The limiting diffusion current density and the starting potential of the different catalysts were tested and the test results are shown in table 1.
TABLE 1 oxygen reduction reaction Performance index (ORR Performance)
As can be seen from Table 1, S-doped NC/Co/Cs 2 The limiting diffusion current density of Se/CoSe catalysts was similar to that of commercial Pt/C catalysts at the initial potential, and the performance of the catalysts obtained in comparative examples 1-10 was relatively poor, indicating that S-doped NC/Co/Cs 2 The Se/CoSe catalyst has better catalytic performance.
Test example 3
Kinetic current density testing (0.8V) was performed on the different catalysts and the test results are shown in table 2.
Table 2 kinetic current density test
As can be seen from Table 2, the S-doped NC/Co/Cs 2 The dynamic current density of Se/CoSe catalysts was higher than that of commercial Pt/C catalysts and the catalysts obtained in comparative examples 1-10, indicating that S was doped with NC/Co/Cs 2 The Se/CoSe catalyst has excellent activity.
Test example 4
The kinetic current density after 10000s of operation of the catalyst was tested, and the current retention rate was calculated by formula 1, and the test results are shown in table 3.
Wherein: η—current retention,%;
J 0 10000s current density, mA.cm -2 ；
J k Initial current density, mA.cm -2 ；
Table 3 evaluation of catalyst stability
Catalyst η/％
Catalyst-1 98.3
Catalyst-2 97.1
Catalyst-3 96.5
Catalyst-4 95.8
Catalyst-5 94.9
Catalyst-6 95.8
D-1 66.3
D-2 59.4
D-3 56.8
D-4 59.1
D-5 49.4
D-6 54.5
D-7 49.9
D-8 54.5
D-9 56.7
D-10 43.5
Commercial Pt/C 81.8
From Table 3, S-doped NC/Co/Cs 2 The Se/CoSe catalysts were excellent in stability, superior to the Pt/C catalysts and the catalysts obtained in comparative examples 1 to 10, indicating that S-doped NC/Co/Cs 2 The Se/CoSe catalyst has better service life.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (8)

1. S-doped NC/Co/Cs 2 The preparation method of the Se/CoSe catalyst is characterized by comprising the following steps:
1) Preparing 2-methylimidazole microemulsion: uniformly dispersing 2-methylimidazole in a first solvent to obtain a dispersed phase; the disperse phase and the continuous phase oil form 2-methylimidazole microemulsion under the emulsification action of an emulsifier and a co-emulsifier; wherein the concentration of the 2-methylimidazole in the disperse phase is 0.1-0.5 mol/L;
2) Subjecting the 2-methylimidazole microemulsion, cobalt salt and cesium salt to a complexation reaction to form Cs x Co 1-x -ZIF; wherein the Cs x Co 1-x The value of x in ZIF is 0<x<1；
3) Causing the Cs to x Co 1-x -the ZIF undergoes an etching reaction with an etchant to produce modified Cs x Co 1-x -ZIF; wherein the etchant is sulfonated humic acid or sulfonated tannic acid;
4) Under nitrogen atmosphere, subjecting the modified Cs x Co 1-x The ZIF reacts with the selenium powder to obtain S doped NC/Co/Cs 2 Se/CoSe catalysts.
2. S-doped NC/Co/Cs according to claim 1 2 The preparation method of the Se/CoSe catalyst is characterized in that the first solvent is deionized water or acetone; the continuous oil phase is one of white oil, kerosene and diesel oil.
3. S-doped NC/Co/Cs according to claim 1 2 The preparation method of the Se/CoSe catalyst is characterized in that the emulsifier is the compound of Span series emulsifier and Tween series emulsifier or the compound of Span series emulsifier and OP series emulsifier; the auxiliary emulsifier is one of n-butanol, propylene glycol and isopropanol.
4. S-doped NC/Co/Cs according to claim 1 2 The preparation method of the Se/CoSe catalyst is characterized in that cobalt salt is cobalt nitrate or cobalt sulfate; the molar ratio of the cobalt salt to the 2-methylimidazole is (2-5): 25, a step of selecting a specific type of material; the cesium salt is cesium nitrate, cesium sulfate or cesium chloride; the molar ratio of the cobalt salt to the 2-methylimidazole is (1-3): 25.
5. s-doped NC/Co/Cs according to claim 1 2 A process for preparing Se/CoSe catalyst, characterized in that the Cs x Co 1-x The mass ratio of ZIF to etchant is 1: (5-10).
6. S-doped NC/Co/Cs according to claim 1 2 A process for preparing Se/CoSe catalyst, characterized by that, the modified Cs x Co 1-x The mass ratio of the ZIF to the selenium powder is 1 (0.8-3).
7. An S-doped NC/Co/Cs prepared by the method of any one of claims 1 to 6 2 Se/CoSe catalysts.
8. An S-doped NC/Co/Cs as claimed in claim 7 2 Se/CoSe catalysts are used for the fuel cell cathode oxygen reduction reaction.
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CN112481653A (en) * 2020-10-29 2021-03-12 浙江大学衢州研究院 Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof
CN115513478A (en) * 2021-06-22 2022-12-23 中国科学院上海硅酸盐研究所 Hollow hierarchical pore carbon nanocage oxygen reduction reaction electrocatalyst and preparation method thereof
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