CN112226780A - NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst - Google Patents

NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst Download PDF

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CN112226780A
CN112226780A CN202011113298.9A CN202011113298A CN112226780A CN 112226780 A CN112226780 A CN 112226780A CN 202011113298 A CN202011113298 A CN 202011113298A CN 112226780 A CN112226780 A CN 112226780A
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graphene oxide
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reduced graphene
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CN112226780B (en
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陈龙
靳鹏飞
李昊泉
李红强
叶嘉惠
方莹
范蕴琪
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Shihezi University
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Abstract

The invention discloses NiCo for full water decomposition2S4The preparation method of the/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is characterized in that the nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is prepared from NiCo2S4Prepared from/N, S-rGO catalyst and prepared NiCo2S4the/N, S-rGO catalyst is used for preparing NiCo by adopting a dispersion method2S4the/N, S-rGO modified working electrode material can be used as an anode and a cathode of full water electrolysis to carry out Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), the overpotential of the full water electrolysis is within 300-600mV, and the material has excellent performance of full water electrolysis and electrocatalysis and is a good bifunctional full water electrolysis catalyst. The method has the advantages of mild reaction conditions, easy control, low cost and the like, can realize high-efficiency electrocatalysis on the full-hydrolyzed water, and has the costLow cost, good stability, small resistivity, simple preparation method and the like.

Description

NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst
Technical Field
The invention relates to the field of new material technology and electrocatalysis, and belongs to the field of polymer chemistry and nano composite materials. In particular to a preparation method of a cobalt-nickel based hydrogen evolution and oxygen evolution electro-catalytic material, and the synthesized NiCo which is fully hydrolyzed2S4the/N, S-rGO bifunctional electrocatalyst has good electrochemical performance.
Background
In the modern society, environmental pollution caused by the dependence on fossil energy, greenhouse effect and energy crisis have attracted extensive attention all over the world, so that the development of a more green new energy technology becomes one of the problems which people need to solve urgently. The hydrogen energy has the advantages of large energy, small density, various forms, convenient transportation, reproducibility, no pollution and the like, is considered as an ideal alternative energy for fundamentally solving global problems of energy, environment and the like, and is known as a final energy. The hydrogen production by electrolyzing water is the most promising hydrogen production technology because of abundant raw material reserves, green, environmental protection and zero carbon emission. And the advantages of simple equipment, convenient maintenance, environmental protection, simple process flow and the like are more and more widely concerned in the methods.
The realization of the hydrogen production process by fully decomposing water mainly depends on the principle of an electrolytic cell, wherein the total decomposition voltage of the electrolytic cell consists of the ideal decomposition voltage of water and the total resistance voltage drop in the electrolytic cell. The total decomposition voltage of the electrolytic cell is a key index for representing the performance of the material, and the larger the decomposition voltage is, the higher the energy consumed by the hydrogen production through water decomposition is. When electrochemical linear sweep voltammetry is adopted for full electrolysis of water and electricity catalysis, two half reactions including OER of an anode and HER of a cathode have higher energy barriers. Therefore, the modified electrode material plays a relatively important role in reducing the energy barrier of the cathode and the anode and improving the catalytic performance.
A commonly used modified electrode material for commercial use at present is Pt/C, RuO2、IrO2However, although electrochemical catalysts prepared based on these materials show good catalytic activity in single OER reaction or HER reaction, their further development is limited by high preparation cost, and catalytic performance in full-hydrolysis hydro-catalysis is not yet optimistic. In order to improve the catalytic performance and the practical application capability of the electrode material, a material with a simple synthesis method, low cost, good catalytic performance and good electrical conductivity needs to be researched and designed to serve as a modified electrode material to be applied to the full-electrolysis water electro-catalytic reaction.
The NiCo is synthesized by a method combining coprecipitation, high-temperature calcination and hydrothermal reaction2S4The synthetic material is used as a bifunctional electrocatalyst of full electrolysis and water electro-catalysis for the first time, and NiCo is synthesized2S4the/N, S-rGO nano composite material has the characteristics of uniform material appearance, uniform particle size distribution and the like.
Disclosure of Invention
The invention aims to provide NiCo for full water decomposition2S4The preparation method of the/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is characterized in that nitrogen and sulfur co-doped reduced graphene oxide and NiCo2S4Prepared from/N, S-rGO catalyst and prepared NiCo2S4the/N, S-rGO catalyst is used for preparing NiCo by adopting a dispersion method2S4the/N, S-rGO modified working electrode material can be used as an anode and a cathode of full water electrolysis to carry out Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), the overpotential of the full water electrolysis is within 300-600mV, and the material has excellent performance of full water electrolysis and electrocatalysis and is a good bifunctional full water electrolysis catalyst. The method has the advantages of mild reaction conditions, easiness in control, low cost and the like, can realize high-efficiency electrocatalysis on the full-hydrolyzed water, and has the advantages of low cost, good stability, small resistivity, simple preparation method and the like.
The invention relates to NiCo for full water decomposition2S4Dual-functional electricity of/nitrogen, sulphur codope reduction oxidation graphite alkeneThe preparation method of the catalyst comprises the following steps:
preparing nitrogen and sulfur co-doped reduced graphene oxide:
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 1-3:1:1, opening an oil bath heating device, adding 10-20mL of 98% concentrated sulfuric acid, opening a stirring device, adding the graphite powder into the concentrated sulfuric acid 3 times, stirring for 10-30min, slowly adding potassium persulfate, uniformly stirring, slowly adding phosphorus pentoxide, reacting at 60-100 ℃ for 4-8h in an oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the product by using a centrifugal machine until the pH of the centrifuged solution is 7, and vacuum-drying the centrifuged product overnight to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 15-30mL of concentrated sulfuric acid, opening a stirring device under the ice bath condition, keeping the temperature at 0 ℃ for 10-30min, adding 1-3g of pre-oxidized graphite obtained in the step a into the stirring device, stirring the pre-oxidized graphite for 10min, adding 3-5g of potassium permanganate in batches, in the process, the temperature of the whole system is kept at 15 ℃, the reaction is carried out for 2 to 4 hours at the temperature of 15 ℃ after the addition is finished, 50 to 100mL of deionized water is added dropwise, the temperature is raised to 20 ℃ and the reaction is carried out for 2 to 4 hours, then 100mL of deionized water and 400mL of hydrogen peroxide with the concentration of 30 percent are added dropwise again for reaction for 0.5 to 2.0 hours, after the reaction is finished and is kept stand overnight, firstly adding 150mL of deionized water, then dropwise adding 30-60mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to be neutral, and freeze-drying to obtain bright yellow graphene oxide;
c. nitrogen and sulfur co-doped reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 1-3 mg.L-1Dispersing in 20-40mL of deionized water, adding 30-80mmol/L of thiourea for dissolving, stirring for 10-30min, transferring into a reaction kettle, and carrying out hydrothermal treatment at the temperature of 150 ℃ and 200 ℃ for 4-10h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. massage deviceWeighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea of 1:2:3-12, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of 0.5-3mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at the temperature of 120-200 ℃ for 4-16h to obtain NiCo2S4Carrying out suction filtration and washing on the/nitrogen and sulfur codoped reduced graphene oxide suspension until the pH value is neutral, collecting, and carrying out vacuum drying at the temperature of 60 ℃ for 12h to obtain NiCo2S4The/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst.
NiCo assembled by one-dimensional nanorods in prepared sample2S4The nano-microspheres are all attached to the surface of the porous flake graphene with the two-dimensional structure.
NiCo obtained by the method2S4The/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is used for carrying out oxygen evolution reaction and hydrogen evolution reaction on an anode and a cathode in the preparation of simultaneous full water decomposition, and the overpotential of the full water decomposition is within 300-600 mV.
NiCo obtained by the method of the invention2S4The catalyst is used for preparing NiCo by adopting a dispersion method2S4the/N, S-rGO modified working electrode material:
preparation of NiCo by dispersion method2S4the/N, S-rGO modified working electrode material:
the obtained NiCo2S4Dispersing the/N, S-rGO composite material in a mixed solution of ethanol, water and polytetrafluoroethylene with the volume ratio of 1-5:1, wherein the volume fraction of the polytetrafluoroethylene is 0.5-20%, ultrasonically dispersing for 30min, and preparing NiCo with the concentration of 0.5-20mg/mL2S4The suspension of/N, S-rGO is coated on foamed nickel and dried to obtain NiCo2S4the/N, S-rGO modified working electrode material, wherein the foamed nickel can be replaced by copper foil, titanium foil or carbon cloth,
drawings
FIG. 1 is a NiCo product of example 3 of the present invention2S4X-ray diffraction pattern of/N, S-rGO;
FIG. 2 is a NiCo product of example 3 of the present invention2S4(ii) transmission electron microscopy images of/N, S-rGO;
FIG. 3 is an OER linear sweep voltammogram of an electrocatalyst according to example 3 of the present invention;
figure 4 is a HER linear sweep voltammogram of the electrocatalyst of example 3 of the invention.
Detailed Description
Example 1
Preparing nitrogen and sulfur co-doped reduced graphene oxide (N, S-rGO):
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 1:1:1, opening an oil bath heating device, adding 10mL of concentrated sulfuric acid with the concentration of 98%, opening a stirring device, adding the graphite powder into the concentrated sulfuric acid for 3 times, stirring for 10min, slowly adding the potassium persulfate, after stirring uniformly, slowly adding the phosphorus pentoxide, reacting at 60 ℃ for 4h under the oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the product by using a centrifugal machine until the pH of the centrifuged solution is 7, and vacuum-drying the centrifuged product overnight to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 15mL of concentrated sulfuric acid, under the ice bath condition, opening a stirring device, keeping the temperature at 0 ℃ for 10min, putting 1g of pre-oxidized graphite obtained in the step a into the stirring device, stirring for 10min, adding 3g of potassium permanganate in batches, keeping the temperature of the whole system at 15 ℃ in the process, reacting at 15 ℃ for 2h after the addition is finished, dropwise adding 50mL of deionized water, heating to 20 ℃ for reacting for 2h, dropwise adding 100mL of deionized water and 3mL of hydrogen peroxide with the concentration of 30% again, reacting for 0.5h, standing overnight after the reaction is finished, firstly adding 150mL of deionized water, dropwise adding 30mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to neutrality, and freeze-drying to obtain bright yellow oxidized graphene;
c. nitrogen, sulfur codopingHetero-reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 1 mg.L-1Dispersing in 20mL of deionized water, adding 30mmol/L thiourea for dissolving, stirring for 10min, transferring into a reaction kettle, and carrying out hydrothermal treatment at 150 ℃ for 4h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. weighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea of 1:2:3, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of 0.5mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at the temperature of 120 ℃ for 4h to obtain NiCo2S4Carrying out suction filtration and washing on the/nitrogen and sulfur codoped reduced graphene oxide suspension until the pH value is neutral, collecting, and carrying out vacuum drying at the temperature of 60 ℃ for 12h to obtain NiCo2S4A/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst;
NiCo assembled by one-dimensional nanorods in prepared sample2S4The nano microspheres are completely attached to the surface of the porous flake graphene with the two-dimensional structure;
preparation of NiCo by dispersion method2S4the/N, S-rGO modified working electrode material:
the obtained NiCo2S4Dispersing the/N, S-rGO catalyst in a mixed solution of ethanol, water and polytetrafluoroethylene with the volume ratio of 1:1, wherein the volume fraction of the polytetrafluoroethylene is 20%, ultrasonically dispersing for 30min, and preparing NiCo with the concentration of 0.5mg/mL2S4The suspension of/N, S-rGO is coated on foamed nickel and dried to obtain NiCo2S4the/N, S-rGO modifies the working electrode material.
Example 2
Preparing nitrogen and sulfur co-doped reduced graphene oxide (N, S-rGO):
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 3:1:1, opening an oil bath heating device, adding 20mL of concentrated sulfuric acid with the concentration of 98%, opening a stirring device, adding the graphite powder into the concentrated sulfuric acid for 3 times, stirring for 30min, slowly adding potassium persulfate, uniformly stirring, slowly adding phosphorus pentoxide, reacting at 100 ℃ for 8h under the oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the products by using a centrifugal machine until the pH of the centrifuged solution is 7, and carrying out vacuum drying overnight on the centrifuged products to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 30mL of concentrated sulfuric acid, under the ice bath condition, opening a stirring device, keeping the temperature at 0 ℃ for 30min, putting 3g of pre-oxidized graphite obtained in the step a into the stirring device, stirring for 10min, adding 5g of potassium permanganate in batches, keeping the temperature of the whole system at 15 ℃ in the process, reacting at 15 ℃ for 4h after the addition is finished, dropwise adding 100mL of deionized water, heating to 20 ℃ for reacting for 4h, dropwise adding 400mL of deionized water and 8mL of hydrogen peroxide with the concentration of 30%, reacting for 2.0h, standing overnight after the reaction is finished, firstly adding 300mL of deionized water, dropwise adding 60mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to be neutral, and freeze-drying to obtain bright yellow oxidized graphene;
c. nitrogen and sulfur co-doped reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 3 mg.L-1Dispersing in 40mL of deionized water, adding 80mmol/L thiourea for dissolving, stirring for 30min, transferring into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 10h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. weighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea of 1:2:12, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at the temperature of 200 ℃ for 16h to obtain NiCo2S4Carrying out suction filtration and washing on the obtained turbid liquid until the pH value is inDrying at 60 deg.C for 12h to obtain NiCo2S4A/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst;
NiCo assembled by one-dimensional nanorods in prepared sample2S4The nano microspheres are completely attached to the surface of the porous flake graphene with the two-dimensional structure;
preparation of NiCo by dispersion method2S4the/N, S-rGO modified working electrode material:
the obtained NiCo2S4Dispersing the/N, S-rGO catalyst in a mixed solution of ethanol, water and polytetrafluoroethylene with the volume ratio of 5:1, wherein the volume fraction of the polytetrafluoroethylene is 0.5%, ultrasonically dispersing for 30min, and preparing NiCo with the concentration of 20mg/mL2S4Coating the suspension on copper foil, and drying to obtain NiCo2S4the/N, S-rGO modifies the working electrode material.
Example 3
Preparing nitrogen and sulfur co-doped reduced graphene oxide (N, S-rGO):
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 2:1:1, taking 10-20mL of 98% concentrated sulfuric acid, opening an oil bath heating device, adding 15mL of 98% concentrated sulfuric acid, opening a stirring device, adding graphite powder into the concentrated sulfuric acid for 3 times, stirring for 20min, slowly adding potassium persulfate, uniformly stirring, slowly adding phosphorus pentoxide, reacting at 80 ℃ for 6h in the oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the product by using a centrifugal machine until the pH of the centrifuged solution is 7, and vacuum-drying the centrifuged product overnight to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 20mL of concentrated sulfuric acid, under the ice bath condition, opening a stirring device, keeping the temperature at 0 ℃ for 20min, putting 2g of pre-oxidized graphite obtained in the step a into the stirring device, stirring for 10min, adding 4g of potassium permanganate in batches, keeping the temperature of the whole system at 15 ℃ in the process, reacting at 15 ℃ for 3h after the addition is finished, dropwise adding 80mL of deionized water, heating to 20 ℃ for reacting for 3h, dropwise adding 200mL of deionized water and 5mL of hydrogen peroxide with the concentration of 30%, reacting for 1.5h, standing overnight after the reaction is finished, firstly adding 200mL of deionized water, dropwise adding 50mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to be neutral, and freeze-drying to obtain bright yellow oxidized graphene;
c. nitrogen and sulfur co-doped reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 2 mg.L-1Dispersing in 30mL of deionized water, adding 50mmol/L thiourea for dissolving, stirring for 20min, transferring into a reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 8h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. weighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea of 1:2:6, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of 2.0mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at 160 ℃ for 12h to obtain NiCo2S4Carrying out suction filtration and washing on the/nitrogen and sulfur codoped reduced graphene oxide suspension until the pH value is neutral, collecting, and carrying out vacuum drying at the temperature of 60 ℃ for 12h to obtain NiCo2S4A/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst;
NiCo assembled by one-dimensional nanorods in prepared sample2S4The nano microspheres are completely attached to the surface of the porous flake graphene with the two-dimensional structure;
preparation of NiCo by dispersion method2S4the/N, S-rGO modified working electrode material:
the obtained NiCo2S4Dispersing the/N, S-rGO catalyst in a mixed solution of ethanol, water and polytetrafluoroethylene with the volume ratio of 3:1, wherein the volume fraction of the polytetrafluoroethylene is 10%, ultrasonically dispersing for 30min, and preparing NiCo with the concentration of 10mg/mL2S4The suspension of/N, S-rGO is coated on the titanium foilDrying to obtain NiCo2S4the/N, S-rGO modifies the working electrode material.
Example 4
Preparing nitrogen and sulfur co-doped reduced graphene oxide (N, S-rGO):
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 2:1:1, opening an oil bath heating device, adding 16mL of concentrated sulfuric acid with the concentration of 98%, opening a stirring device, adding the graphite powder into the concentrated sulfuric acid for 3 times, stirring for 15min, slowly adding potassium persulfate, uniformly stirring, slowly adding phosphorus pentoxide, reacting at 90 ℃ for 5h under the oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the products by using a centrifugal machine until the pH of the centrifuged solution is 7, and carrying out vacuum drying overnight on the centrifuged products to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 25mL of concentrated sulfuric acid, under the ice bath condition, opening a stirring device, keeping the temperature at 0 ℃ for 25min, placing 2.5g of pre-oxidized graphite obtained in the step a into the stirring device, stirring for 10min, adding 4g of potassium permanganate in batches, keeping the temperature of the whole system at 15 ℃ in the process, reacting at 15 ℃ for 3h after the addition is finished, dropwise adding 70mL of deionized water, heating to 20 ℃ for reacting for 2h, dropwise adding 400mL of deionized water and 8mL of hydrogen peroxide with the concentration of 30%, reacting for 2.0h, standing overnight after the reaction is finished, firstly adding 250mL of deionized water, dropwise adding 45mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to neutrality, and freeze-drying to obtain bright yellow oxidized graphene;
c. nitrogen and sulfur co-doped reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 2 mg.L-1Dispersing in 40mL of deionized water, adding 60mmol/L thiourea for dissolving, stirring for 25min, transferring into a reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 7h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. weighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea of 1:2:9, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of 3mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at the temperature of 180 ℃ for 10h to obtain NiCo2S4Carrying out suction filtration and washing on the/nitrogen and sulfur codoped reduced graphene oxide suspension until the pH value is neutral, collecting, and carrying out vacuum drying at the temperature of 60 ℃ for 12h to obtain NiCo2S4A/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst;
NiCo assembled by one-dimensional nanorods in prepared sample2S4The nano microspheres are completely attached to the surface of the porous flake graphene with the two-dimensional structure;
preparation of NiCo by dispersion method2S4the/N, S-rGO modified working electrode material:
the obtained NiCo2S4Dispersing the/N, S-rGO composite material in a mixed solution of ethanol, water and polytetrafluoroethylene with the volume ratio of 4:1, wherein the volume fraction of the polytetrafluoroethylene is 15%, ultrasonically dispersing for 30min to prepare NiCo with the concentration of 5mg/mL2S4Coating the suspension on carbon cloth, and drying to obtain NiCo2S4the/N, S-rGO modifies the working electrode material.
Example 5
Example 1-NiCo obtained in example 42S4NiCo prepared by a dispersion method through a/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst2S4the/N, S-rGO modified working electrode material is used in full-electrolysis water electro-catalysis and comprises the following steps:
the electro-catalysis equipment adopts a three-electrode system and consists of an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode and a reference electrode; platinum wire is used as a counter electrode, silver/silver chloride is used as a reference electrode, a working electrode is formed by using foamed nickel as a substrate and NiCo2S4the/N, S-rGO modified working electrode material is a working electrode, and the electrolyte in the electrolytic cell is KOH solution with the concentration of 1-5 mol/L; need to supply electricityIntroducing pure O into the hydrolyzed solution2Making it reach oxygen saturation state, introducing O2The time of (2) is 20-60 min; the foamed nickel electrode can be replaced by a graphite electrode, a glassy carbon electrode, a copper foil or a titanium foil;
the electrocatalysis method mainly adopts a linear sweep voltammetry method, and related detection parameters are as follows: the standing time is set to be 1-10s, the scanning rate is 0.5-100mV/s, and the scanning range is 1.0-2.2V.
The method of the invention obtains NiCo2S4the/N, S-rGO modified working electrode material can be used as an anode and a cathode of full water decomposition to carry out Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), the full water decomposition overpotential is within 300-600mV, and the results show that: NiCo2S4The modified working electrode material is uniformly loaded on the surface of N, S-rGO, has good bifunctional catalytic activity of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), has relatively excellent catalytic activity and stability when being applied to full water electrolysis, and is an electrolyzed water catalyst material with excellent performance.

Claims (3)

1. NiCo for full water decomposition2S4The preparation method of the/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is characterized by comprising the following steps of:
preparing nitrogen and sulfur co-doped reduced graphene oxide:
a. pre-oxidizing graphene: weighing graphite powder, potassium persulfate and phosphorus pentoxide in a mass ratio of 1-3:1:1, opening an oil bath heating device, adding 10-20mL of 98% concentrated sulfuric acid, opening a stirring device, adding the graphite powder into the concentrated sulfuric acid 3 times, stirring for 10-30min, slowly adding potassium persulfate, uniformly stirring, slowly adding phosphorus pentoxide, reacting at 60-100 ℃ for 4-8h in an oil bath state, adding a small amount of concentrated sulfuric acid in the process to keep the reaction system in a solution state, standing overnight at room temperature after the reaction is finished, slowly adding water to dilute all reactants into a solution state, centrifugally washing the product by using a centrifugal machine until the pH of the centrifuged solution is 7, and vacuum-drying the centrifuged product overnight to obtain grey pre-oxidized graphene;
b. oxidation of graphene: measuring 15-30mL of concentrated sulfuric acid, opening a stirring device under the ice bath condition, keeping the temperature at 0 ℃ for 10-30min, adding 1-3g of the pre-oxidized graphite obtained in the step a, stirring for 10min, adding 3-5g of potassium permanganate for 3 times, in the process, the temperature of the whole system is kept at 15 ℃, the reaction is carried out for 2 to 4 hours at the temperature of 15 ℃ after the addition is finished, 50 to 100mL of deionized water is added dropwise, the temperature is raised to 20 ℃ and the reaction is carried out for 2 to 4 hours, then 100mL of deionized water and 400mL of hydrogen peroxide with the concentration of 30 percent are added dropwise again for reaction for 0.5 to 2.0 hours, after the reaction is finished and is kept stand overnight, firstly adding 150mL of deionized water, then dropwise adding 30-60mL of concentrated hydrochloric acid, centrifugally washing the whole reaction system to be neutral, and freeze-drying to obtain bright yellow graphene oxide;
c. nitrogen and sulfur co-doped reduced graphene oxide: c, enabling the graphene oxide obtained in the step b to be 1-3 mg.L-1Dispersing in 20-40mL of deionized water, adding 30-80mmol/L of thiourea for dissolving, stirring for 10-30min, transferring into a reaction kettle, and carrying out hydrothermal treatment at the temperature of 150 ℃ and 200 ℃ for 4-10h to obtain nitrogen and sulfur co-doped reduced graphene oxide;
NiCo2S4preparation of a/N, S-rGO catalyst:
d. weighing cobalt nitrate, nickel nitrate and thiourea according to the molar ratio of Ni to Co to thiourea =1 to 2 to 3-12, dissolving the cobalt nitrate, the nickel nitrate and the thiourea in deionized water to form a mixed solution with the concentration of 0.5-3mol/L, dispersing the nitrogen and sulfur Co-doped reduced graphene oxide obtained in the step c in the mixed solution, fully stirring for 30min, putting the mixed solution into a hydrothermal kettle, and carrying out hydrothermal treatment at the temperature of 120-200 ℃ for 4-16h to obtain NiCo2S4Carrying out suction filtration and washing on the/nitrogen and sulfur codoped reduced graphene oxide suspension until the pH value is neutral, collecting, and carrying out vacuum drying at the temperature of 60 ℃ for 12h to obtain NiCo2S4The/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst.
2. NiCo for total water splitting according to claim 12S4The preparation method of the/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is characterized in that NiCo assembled by one-dimensional nanorods in a prepared sample2S4The nano-microspheres are all attached to the surface of the porous flake graphene with the two-dimensional structure.
3. NiCo obtained by the process according to claim 12S4The/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst is used for carrying out oxygen evolution reaction and hydrogen evolution reaction on an anode and a cathode in the preparation of simultaneous full water decomposition, and the overpotential of the full water decomposition is within 300-600 mV.
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