CN115125575B - Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst of (2) and preparation method and application thereof - Google Patents

Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst of (2) and preparation method and application thereof Download PDF

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CN115125575B
CN115125575B CN202210813679.0A CN202210813679A CN115125575B CN 115125575 B CN115125575 B CN 115125575B CN 202210813679 A CN202210813679 A CN 202210813679A CN 115125575 B CN115125575 B CN 115125575B
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cobalt
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林绪亮
薛李静
邱学青
秦延林
陈理恒
俎喜红
张文礼
林煜翔
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Guangdong University of Technology
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Abstract

The invention relates to a sulfur-nitrogen doped carbon-coated Co 9 S 8 ‑Ni 3 S 2 A catalyst, a preparation method and application thereof. The invention utilizes the characteristic that lignosulfonate and transition metal ions have stronger coordination capability, takes lignosulfonate as a carbon source and a sulfur source, takes urea and the like as a nitrogen source, mixes lignosulfonate with cobalt salt and nickel salt to obtain a mixed solution, and adjusts the pH value of the mixed solution to enable Co and Ni metal ions to be in an optimal coordination environment, and further carries out freeze drying, thereby obtaining a lignin-based metal compound, finally mixes the compound with the nitrogen source and carries out carbonization treatment, and designs sulfur and nitrogen doped carbon coated Co 9 S 8 ‑Ni 3 S 2 The catalyst has good stability, higher OER catalytic activity of the electrolyzed water, simple preparation process, low cost and more environmental friendliness.

Description

Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst of (2) and preparation method and application thereof
Technical Field
The invention relates to the technical field of biomass-based materials and electrocatalytic materials, in particular to a sulfur-nitrogen doped carbon-coated Co 9 S 8 -Ni 3 S 2 A preparation method and application thereof.
Background
Depletion of fossil fuels and global warming have prompted the development of renewable and clean energy sources. Zero pollution, high specific energy density and rich source of hydrogen energy are the most traditional fossil fuelOne of the potential alternatives. Water electrolysis technology has become an important sustainable hydrogen production technology. Oxygen Evolution Reaction (OER) is an important half-reaction of the electrochemical process efficiency of electrochemical devices due to the inherent reaction retardation and excessive formation of the reaction energy barrier during proton coupled electron transfer. The development of catalyst materials for OER can effectively solve the bottleneck problem in the practical application of these technologies. Currently, under basic conditions, noble metal-based compounds (e.g., irO 2 And RuO (Ruo) 2 ) Is the most effective OER catalyst, but because of scarce resources and high cost limit its commercial application, there is an urgent need to develop efficient transition metal-based OER electrocatalysts to accelerate the reaction process, reduce overpotential and improve conversion efficiency.
3d transition metal based materials are widely studied for their abundant earth resources and cost-effective advantages, especially for oxides, nitrides, sulfides and di-hydroxides. Among them, transition metal chalcogenides are of particular interest due to the presence of their abundant redox couple, which is advantageous for increasing the intrinsic activity in electrochemical reactions. Co, in particular as electrocatalyst 9 S 8 And Ni 3 S 2 And has attracted extensive attention. Co (Co) 9 S 8 Due to its excellent redox capacity, OER electrocatalysts have proven to be a very promising; and Ni 3 S 2 Due to their abundant valence states, rapid electron transfer rates, and abundant active sites, have been identified as potential catalysts for various electrochemical reactions. However, single transition metal sulfides as OER electrocatalysts may suffer from low stability, low intrinsic conductivity and relatively low active surface area.
To solve the above problems, co is used as 9 S 8 And Ni 3 S 2 The composite material of the composition can improve intrinsic conductivity, higher level of morphological structure, more active sites and possible synergistic effect. Heteroatom doped carbon materials are commonly used in the art for encapsulating Co 9 S 8 Or Ni 3 S 2 On the one hand, the heteroatom doped carbon material not only has better conductivity and long termDurability, also can be used as a shell to protect metal sulfides from aggregation, on the other hand heteroatom doping can tailor the electronic structure of the catalyst, thereby enhancing the electrocatalytic activity of the catalyst. However, co 9 S 8 And Ni 3 S 2 Are still unsatisfactory due to instability, severe aggregation during synthesis, and low conductivity, and heteroatom doped carbon-coated Co 9 S 8 And Ni 3 S 2 The synthesis of the catalyst is not only complicated in process and complicated in steps, but also requires the use of sulfur sources harmful to the environment, such as: sulfur powder, thioacetamide, na 2 S, thiourea and the like are not suitable for large-scale industrial application from both economical and ecological viewpoints.
Disclosure of Invention
The invention aims to solve the problems of Co in the prior art 9 S 8 And Ni 3 S 2 The composite material has the problems of instability, low conductivity and the like, thereby providing a sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 The catalyst and the preparation method thereof have the advantages of good stability, higher OER catalytic activity of the electrolyzed water, simple preparation process, low cost and more environmental friendliness.
To achieve the above object, the present invention is achieved by the following means:
the first aspect of the invention provides a sulfur-nitrogen doped carbon-coated Co 9 S 8 -Ni 3 S 2 The preparation method of the catalyst comprises the following steps:
(1) Preparing a mixed solution containing lignosulfonate, cobalt salt and nickel salt, and uniformly stirring;
(2) Regulating the pH value of the mixed solution obtained in the step (1), and then performing freeze drying treatment to obtain a lignin-based metal compound;
(3) Mixing the lignin-based metal compound with a nitrogen source, and carbonizing in a protective atmosphere.
Preferably, the lignosulfonate in the step (1) is selected from one or more of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate and magnesium lignosulfonate; most preferably, the lignosulfonate is selected from sodium lignosulfonate.
Preferably, the cobalt salt in step (1) is selected from one or more of cobalt chloride, cobalt nitrate and cobalt sulfate.
Preferably, the nickel salt in step (1) is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel oxalate.
Preferably, the molar mass ratio of nickel ions to cobalt ions in the mixed solution in the step (1) is 1:0.1-8; most preferably, the molar mass ratio of nickel ions to cobalt ions is 1:7.
Preferably, the amount of lignosulfonate in the mixed solution in step (1) satisfies the following condition: the total molar mass of cobalt ions and nickel ions in the mixed solution containing 1g of lignosulfonate is 6-15mmol; most preferably, the amount of lignosulfonate in the mixed solution in step (1) satisfies the following condition: the total molar mass of cobalt ions and nickel ions in the mixed solution containing 1g of lignosulfonate was 6-10mmol.
Preferably, the pH is adjusted to 4-8 in step (2); most preferably, the pH is adjusted to 8.
Preferably, the temperature of the freeze-drying treatment in the step (2) is 0.5-0.8 ℃ for 3-4 days; most preferably, the freeze-drying is carried out at a temperature of 0.6 ℃ for a period of 3 days.
Preferably, the nitrogen source in step (3) is selected from one or more of urea, dicyandiamide, melamine and chitosan.
Preferably, the mass ratio of the lignin-based metal complex to the nitrogen source in step (3) is 1:1-6.
Preferably, the protective atmosphere in the step (3) is selected from one or more of nitrogen, argon and helium; most preferably, the protective atmosphere is selected from nitrogen.
Preferably, the carbonization treatment in the step (3) is carried out at a temperature of 700-900 ℃ for 2-3 hours; most preferably, the carbonization treatment is carried out at a temperature of 800 ℃ for a time of 2 hours.
The second aspect of the invention provides sulfur-and nitrogen-doped carbon-coated Co prepared by the preparation method 9 S 8 -Ni 3 S 2 A catalyst.
The third aspect of the invention provides sulfur-and nitrogen-doped carbon-coated Co prepared by the preparation method 9 S 8 -Ni 3 S 2 The catalyst is applied to electrolytic water oxygen evolution reaction.
Lignosulfonate (LS), a byproduct of the pulp and paper industry, is an aromatic oligomer with sulfonate groups. The coexistence of carbon and elemental sulfur makes LS a renewable carbon and sulfur precursor for the preparation of sulfur/carbon-based materials. The invention utilizes the characteristic that sodium lignosulfonate and transition metal ions have stronger coordination capability, takes lignosulfonate as a carbon source and a sulfur source, takes urea and the like as a nitrogen source, mixes sodium lignosulfonate with cobalt salt and nickel salt to obtain a mixed solution, ensures that Co and Ni metal ions are in an optimal coordination environment by adjusting the pH value of the mixed solution, and further carries out freeze drying to obtain a lignin-based metal compound, finally mixes the compound with the nitrogen source and carries out carbonization treatment to design sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 A catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, after being doped with the nonmetallic element S, N, a core-shell structure is formed with C in situ, and metal active substances such as metal sulfide are coated, so that the active substances are prevented from agglomerating and the dispersibility of the metal is changed;
(2) The catalyst prepared by the method has higher electrolytic water OER catalytic activity, and the current density is 10mA cm -2 When the OER overpotential is lower than 200mV, the catalyst can be used as an electrolytic water OER catalyst.
(3) The preparation method disclosed by the invention is simple in flow, low in cost, green, environment-friendly and sustainable, and has a wide market application prospect.
Drawings
FIG. 1 is an XRD pattern of the catalyst prepared in example 1.
FIG. 2 is an SEM image of the catalyst prepared in example 1.
FIG. 3 is a TEM image of the catalyst prepared in example 1.
FIG. 4 is a graphical representation of OER test results for the catalysts obtained in examples 1-3.
FIG. 5 is a graphical representation of OER test results for the catalysts obtained from example 1 and comparative examples 1-5.
FIG. 6 shows the current density of the catalyst prepared in example 1 at 50 mA.cm -2 OER stability results at time are shown schematically.
FIG. 7 shows the current density of the catalysts prepared in comparative example 2, comparative example 3 and comparative example 5 at 50mA cm -2 OER stability results at time are shown schematically.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 The preparation method of the catalyst comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total molar amount of cobalt ion and nickel ion was 8 mmol) was added to 50mLMagnetic stirring is carried out uniformly in pure water, and the mixture is added into a sodium lignin sulfonate aqueous solution dropwise, and stirring is carried out for 10min to obtain a mixed solution (the molar ratio of nickel ions to cobalt ions in the mixed solution is 1:7);
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-based metal complex solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-based metal complex;
(3) Mixing 0.5g of lignin-based metal compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-based metal compound.
The prepared sulfur and nitrogen doped carbon coated Co is respectively adopted by an X-ray diffractometer, a scanning electron microscope and a transmission electron microscope 9 S 8 -Ni 3 S 2 The morphology of the catalyst was examined and the results are shown in FIGS. 1-3, respectively. Wherein FIG. 1 is a sulfur-nitrogen doped carbon-coated Co 9 S 8 -Ni 3 S 2 As can be seen from FIG. 1, the XRD pattern of the catalyst has a phase composition of Co 9 S 8 、Ni 3 S 2 Are active substances in OER process in the catalytic process. FIG. 2 is a sulfur-nitrogen doped carbon-coated Co 9 S 8 -Ni 3 S 2 SEM image of the catalyst. As can be seen from fig. 2, the catalyst prepared is porous and has a large number of macropores and mesopores, and the structure can provide and expose more active sites. FIG. 3 is a sulfur-nitrogen doped carbon-coated Co 9 S 8 -Ni 3 S 2 As can be seen from the TEM image of the catalyst in fig. 3, the prepared catalyst has a typical core-shell structure, and carbon is coated with metal active materials, so that agglomeration of metal is avoided, the active materials are uniformly dispersed, active sites are increased, and thus, the catalytic reaction performance is improved.
Example 2
Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Is a catalyst of (1)The preparation method comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total mole amount of cobalt ions and nickel ions is 8 mmol) is added into 50mL of pure water, magnetic stirring is carried out uniformly, and the mixture is added into sodium lignin sulfonate aqueous solution dropwise, and stirring is carried out for 10min to obtain mixed solution (mole ratio of nickel ions and cobalt ions in the mixed solution is 1:0.14);
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-based metal complex solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-based metal complex;
(3) Mixing 0.5g of lignin-based metal compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-based metal compound.
Example 3
Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 The preparation method of the catalyst comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total mole amount of cobalt ions and nickel ions is 8 mmol) is added into 50mL of pure water, magnetic stirring is carried out uniformly, and the mixture is added into sodium lignin sulfonate aqueous solution dropwise, and stirring is carried out for 10min to obtain mixed solution (mole ratio of nickel ions and cobalt ions in the mixed solution is 1:0.3);
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-based metal complex solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-based metal complex;
(3) Mixing 0.5g of lignin-based metal compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-based metal compound.
Comparative example 1
Sulfur and nitrogen doped carbon coated Co 9 S 8 The preparation method of the catalyst comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) (total molar quantity of cobalt ions is 8 mmol) is added into 50mL of pure water, and the mixture is stirred evenly by magnetic force and added into sodium lignin sulfonate aqueous solution dropwise, and the mixture is stirred for 10min to obtain a mixed solution;
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-cobalt composite precursor solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-cobalt composite;
(3) Mixing 0.5g of lignin-cobalt compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-cobalt composite.
Comparative example 2
Sulfur and nitrogen doped carbon coated Ni 3 S 2 The preparation method of the catalyst comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total molar quantity of nickel ions is 8 mmol) is added into 50mL of pure water, and the mixture is stirred evenly by magnetic force and added into sodium lignin sulfonate aqueous solution dropwise, and the mixture is stirred for 10min to obtain a mixed solution;
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-nickel composite precursor solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-nickel composite;
(3) Mixing 0.5g of lignin-cobalt compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-cobalt composite.
Comparative example 3
Sulfur-doped carbon-coated Co 9 S 8 -Ni 3 S 2 The preparation method of the catalyst comprises the following steps:
(1) 1.0g of sodium lignin sulfonate was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total molar quantity of cobalt ions and nickel ions is 8 mmol) is added into 50mL of pure water, magnetic stirring is carried out uniformly, and the mixture is added into sodium lignin sulfonate aqueous solution dropwise, and stirring is carried out for 10min to obtain mixed solution (molar ratio of nickel ions and cobalt ions in the mixed solution is 1:7);
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-based metal complex solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-based metal complex;
(3) And (3) performing high-temperature charcoal burning on the lignin-based metal compound to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling the sample to room temperature, respectively washing with 1mol/L hydrochloric acid solution and deionized water, and drying at 80 ℃ for 12 hours to obtain the lignin-based metal compound.
Comparative example 4
A catalyst comprising cobalt nickel bi-metal, the method of preparation comprising the steps of:
(1) Cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total molar amount of cobalt ion and nickel ion is 8 mmol) was added to 100mL of pure water, and stirred for 10min to obtainMixed solution (the mole ratio of nickel ions and cobalt ions in the mixed solution is 1:7);
(2) Regulating the pH of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain a metal compound solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain a metal compound;
(3) Mixing 0.5g of metal compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, performing carbonization treatment at 800 ℃ for 2 hours, cooling a sample to room temperature, respectively washing with 1mol/L hydrochloric acid solution and deionized water, and drying at 80 ℃ for 12 hours to obtain the composite.
Comparative example 5
The preparation method of the nitrogen-doped carbon cobalt nickel bimetallic catalyst comprises the following steps:
(1) 1.0g of alkali lignin was weighed into 50mL of pure water, and cobalt nitrate hexahydrate (Co (NO) 3 ） 2 ·6H 2 O) and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) (total molar quantity of cobalt ions and nickel ions is 8 mmol) is added into 50mL of pure water, magnetic stirring is carried out uniformly, and the mixture is added into sodium lignin sulfonate aqueous solution dropwise, and stirring is carried out for 10min to obtain mixed solution (molar ratio of nickel ions and cobalt ions in the mixed solution is 1:1);
(2) Regulating the pH value of the mixed solution to 8 by ammonia water and HCl, continuously stirring for 10min to obtain lignin-based metal complex solution, then freeze-drying at 0.6 ℃ for 3 days, and grinding the obtained sample to obtain lignin-based metal complex;
(3) Mixing 0.5g of lignin-based metal compound with 0.5g of urea, performing high-temperature charcoal burning to 800 ℃ in a nitrogen atmosphere by a thermal stabilization procedure, carbonizing at 800 ℃ for 2 hours, cooling a sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the lignin-based metal compound.
Verification example 1
The catalysts prepared in examples 1 to 3 and comparative examples 1 to 5 were used for testing electrochemical properties. Electrochemical performance testing was performed on a Gamry Interface 1010 electrochemical workstation using conventional methodsA three-electrode system, a spectrally pure graphite rod (purity 99.999%) was used as a counter electrode and Hg/HgO as a reference electrode. The working electrode is prepared by a 'dripping method', namely adding 4mg of catalyst powder into 200 mu L of 0.25% Nafion-ethanol solution, performing ultrasonic dispersion for 15min, sucking 50 mu L of sample dispersion liquid drop on foam nickel (0.5X0.5 mm), respectively ultrasonically cleaning the foam nickel with acetone, 3M HCl, ethanol and deionized water for 30min before dripping, and drying under nitrogen atmosphere at 60 ℃ to obtain the catalyst with the loading capacity of 4.0 mg.cm -2 。
The electrochemical performance test is carried out in KOH electrolyte solution of 1M, high-purity oxygen is continuously introduced during OER test, and the potentials are compensated by IR through the self-contained Thale software of the instrument. Measurement of polarization Curve by Linear sweep voltammetry, oxygen evolution reaction at 0V as initial potential, at 2 mV s -1 Is scanned to 1V. The electrocatalytic activity of the catalyst was measured in a standard three electrode system, with the auxiliary electrode replaced by a spectrally pure graphite rod in order to exclude the potential gain effect of Pt on the catalyst.
The detection results are shown in FIG. 4 and Table 1. The results showed that the current density was 10mA cm -2 When the OER overpotential of example 1 was 200mV, the OER overpotential of example 2 was 200mV, and the OER overpotential of example 3 was 220mV, indicating that the metal doping amount had an effect on the OER catalytic performance of the catalyst of the present invention.
The detection results are shown in FIG. 5 and Table 1. The results showed that the current density was 10mA cm -2 At 240mV for the OER overpotential of comparative example 1, 370mV for comparative example 2, 330mV for comparative example 3, 355mV for comparative example 4 and 350mV for comparative example 5, the catalytic performance of the catalyst obtained in example 1 is inferior to that of the catalyst obtained in example 1 because the catalyst obtained in comparative example 1 is Co only 9 S 8 The catalyst obtained in comparative example 2 was Ni alone 3 S 2 The catalyst obtained in comparative example 3 was doped with sulfur only. Comparative example 4 no lignosulfonate was used as a sulfur source and a carbon source for preparing a catalyst, and the resulting catalyst did not form Co 9 S 8 And Ni 3 S 2 . In comparative example 5, alkali lignin was used insteadThe catalyst prepared by the substituted lignin sulfonate has no sulfur source and can not form Co 9 S 8 And Ni 3 S 2 。
Verification example 2
The catalyst prepared in example 1 was subjected to stability test, and the test results are shown in fig. 6. The results show that the catalyst prepared in example 1 has a current density of 50mA cm -2 And after 50h of stability test, the potential of the sample is basically unchanged, and the sample shows good stability. As shown in FIG. 7, the catalysts prepared in comparative example 2, comparative example 3 and comparative example 5 had a current density of 50 mA.cm -2 Under the test of 50 hours stability, the potential of the sample is increased, which indicates that the stability of the catalyst is poor.
TABLE 1 Current Density of 10mA cm -2 Time OER overpotential
OER overpotential/mV
Example 1 200
Example 2 200
Example 3 220
Comparative example 1 240
Comparative example 2 370
Comparative example 3 330
Comparative example 4 355
Comparative example 5 350
The above detailed description describes the analysis method according to the present invention. It should be noted that the above description is only intended to help those skilled in the art to better understand the method and idea of the present invention, and is not intended to limit the related content. Those skilled in the art may make appropriate adjustments or modifications to the present invention without departing from the principle of the present invention, and such adjustments and modifications should also fall within the scope of the present invention.

Claims (5)

1. Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 The preparation method of the catalyst is characterized by comprising the following steps:
(1) Preparing a mixed solution containing sodium lignin sulfonate, cobalt salt and nickel salt, and uniformly stirring; the molar ratio of nickel ions to cobalt ions in the mixed solution is 1:0.1-8; the dosage of the sodium lignin sulfonate in the mixed solution meets the following conditions: the total mass of cobalt ions and nickel ions in the mixed solution containing 1g of sodium lignin sulfonate is 6-15mmol;
(2) Regulating the pH value of the mixed solution obtained in the step (1), and then performing freeze drying treatment to obtain a lignin-based metal compound;
(3) Mixing the lignin-based metal compound with a nitrogen source, and carbonizing in a protective atmosphere to obtain the lignin-based metal compound; the mass ratio of the lignin-based metal complex to the nitrogen source is 1:1-6; the nitrogen source is selected from one or more of urea, dicyandiamide, melamine and chitosan.
2. The method according to claim 1, wherein the cobalt salt in step (1) is one or more selected from the group consisting of cobalt chloride, cobalt nitrate and cobalt sulfate.
3. The method according to claim 1, wherein the nickel salt in step (1) is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate, and nickel oxalate.
4. A sulfur-and nitrogen-doped carbon-coated Co prepared by the method of any one of claims 1-3 9 S 8 -Ni 3 S 2 A catalyst.
5. A sulfur-and nitrogen-doped carbon-coated Co prepared by the method of any one of claims 1-3 9 S 8 -Ni 3 S 2 The catalyst is applied to electrolytic water oxygen evolution reaction.
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CN109012590B (en) * 2018-08-24 2020-04-07 华南理工大学 Lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof
CN110201682A (en) * 2019-05-23 2019-09-06 东华大学 Cobalt sulfide nickel nitrogen-doped carbon nano-fiber composite material and preparation method and application
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