CN117265572A - Preparation method of cerium doped nickel sulfide catalyst and electrochemical application thereof - Google Patents

Preparation method of cerium doped nickel sulfide catalyst and electrochemical application thereof Download PDF

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Publication number
CN117265572A
CN117265572A CN202310062261.5A CN202310062261A CN117265572A CN 117265572 A CN117265572 A CN 117265572A CN 202310062261 A CN202310062261 A CN 202310062261A CN 117265572 A CN117265572 A CN 117265572A
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China
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doped nickel
catalyst
cerium
nickel sulfide
sulfide catalyst
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薛辉
田碧莹
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Inner Mongolia University
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Inner Mongolia University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water

Abstract

The invention prepares cerium doped nickel sulfide catalyst with carbon cloth as substrate and researches the application of the catalyst in oxygen evolution and urea oxidation reaction. Firstly, synthesizing a cerium-doped nickel hydroxide precursor on carbon cloth by taking nickel nitrate, cerium nitrate, urea and ammonium fluoride as raw materials through a hydrothermal method, and then doping sulfur element by utilizing a high-temperature controllable heat treatment method to synthesize the efficient and stable cerium-doped nickel sulfide electrocatalyst. The catalyst has excellent electrochemical performance, low operating voltage of oxygen evolution and urea oxidation reaction, small Tafil slope and oxygen evolution reaction of 10 mA/cm only with 1.40. 1.40V 2 The tafel slope was 40.2 mV/dec; the urea oxidation reaction can reach 10 mA/cm only by 1.28 and 1.28V 2 The tafel slope was 58.3 mV/dec. The catalyst can be repeatedly used for thousands of times, and the performance of the catalyst is still stable, which shows that the catalyst has good long-term stability, thus the catalyst has good electrochemical related fieldsIs a popularization and application prospect.

Description

Preparation method of cerium doped nickel sulfide catalyst and electrochemical application thereof
Technical Field
The invention belongs to the field of electrocatalytic nano materials, and particularly relates to a preparation method of a cerium-doped nickel sulfide electrocatalytic material and application of the cerium-doped nickel sulfide electrocatalytic material in electrolytic water and urea electrooxidation reaction.
Background
Electrocatalytic Oxygen Evolution Reactions (OER) play a considerable role in many renewable energy conversion and storage devices, such as direct fuel cells, hydrogen plants, metal air cells, and the like. However, the efficiency of these energy conversion devices is greatly limited by the slow kinetic steps of OER. In contrast to the high thermodynamic potential of OER (1.23V), urea oxidation (UOR, CO (NH) 2 ) 2 + 6OH - → N 2 + 5 H 2 O + CO 2 + 6e - ) Has extremely low thermodynamic potential barrier (0.37V), is ideal reverse for replacing OERShould be used as an anode reaction in the novel energy conversion device. However, the smooth operation of UOR requires additional energy to overcome the reaction barrier caused by its multiple electron transfer pathways and complex reaction intermediate formation/desorption processes. Therefore, the reaction rate is improved, the activation energy of the intermediate is reduced, and the design of the OER and UOR electrocatalyst with excellent synthesis performance has important practical significance by optimizing a synthesis strategy.
Currently, transition metal nickel-based materials, including hydroxides, oxides and sulfides, are considered to be a class of excellent catalysts for OER and UOR. Sulfide has high conductivity and rich oxidation-reduction chemical property, has various structures, is expected to become an ideal substitute for noble metal catalysts, and has important significance in developing novel sulfide materials for OER and UOR. Research shows that the heteroatom doping can effectively regulate the electronic structure of the active site and improve the activation capability of the reactant. In recent years, rare Earth (RE) elements have received attention because of their flexible vacancy-generating capability and unique chemical, electronic properties of the 4 f-sub-shell orbitals. The rare earth metal ions as dopants can generate more vacancies in the host material, improving the catalytic activity. Meanwhile, rare earth metals have multiple valence electron orbitals, so that the rare earth metals have variable coordination numbers and geometric configurations. Therefore, the electronic structure and the vacancy of the transition metal sulfide are regulated and controlled through rare earth ion doping, and a feasible scheme is provided for designing and synthesizing the high-activity OER and UOR catalysts.
Disclosure of Invention
The invention aims to provide a preparation method of a cerium doped nickel sulfide catalyst and application of the cerium doped nickel sulfide catalyst in electrolytic water and urea oxidation, and application research results show that the catalyst has excellent oxygen evolution, urea oxidation electrocatalytic activity and good chemical stability. The material is a cerium doped nickel sulfide composite material synthesized by a simple hydrothermal method and a high-temperature vulcanization method. The invention aims at realizing the following technical scheme:
firstly, respectively weighing a certain amount of nickel nitrate, cerium nitrate, urea and ammonium fluoride according to a certain raw material ratio, respectively placing the nickel nitrate, the cerium nitrate, the urea and the ammonium fluoride in four beakers, respectively weighing a certain amount of deionized water, respectively adding the deionized water into the four beakersStirring for 30 minutes to fully dissolve the materials, pouring the solution in the four beakers into another beaker for mixing, stirring for 30 minutes to fully mix the solution, then placing the treated carbon cloth and the dissolved mixed solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into a baking oven, reacting at 120 ℃ for 12 h to obtain a cerium-doped nickel hydroxide precursor loaded on the carbon cloth, taking out the reacted carbon cloth, washing the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and drying the carbon cloth. Then, the cerium doped nickel hydroxide precursor loaded by carbon cloth is placed at the position of the tail end of a porcelain boat, sulfur powder is weighed and placed at the position of the front end of the same porcelain boat, and the porcelain boat is placed in a tube furnace to react at 350 ℃ in a nitrogen atmosphere for 2 h, so that the cerium doped nickel sulfide catalyst is obtained. The catalyst can reach 10 mA/cm only by 1.40. 1.40V when in anodic electrolysis in 1M KOH solution 2 The tafel slope was 40.2 mV/dec; when the anode is electrolyzed in a mixed solution of 1M KOH and 0.5. 0.5M urea, the anode can reach 10 mA/cm only by 1.28. 1.28V 2 The tafel slope was 58.3 mV/dec. Meanwhile, polarization curves can be basically overlapped after 1000 CV cycles, and the catalyst can still keep stable performance after 80 h is used in the two solutions. The test result shows that the catalyst of the invention is expected to be used in electrocatalytic oxygen evolution and urea oxidation reactions.
The invention has the advantages that:
the cerium-doped nickel sulfide catalyst prepared by the method has high-efficiency OER and UOR performances, and is an efficient oxygen evolution and urea oxidation reaction catalyst.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cerium doped nickel sulfide catalyst precursor and a cerium doped nickel sulfide catalyst;
FIG. 2 is a scanning electron microscope image of a cerium doped nickel sulfide catalyst;
FIG. 3 is an energy dispersive X-ray spectrometer imaging diagram of a cerium doped nickel sulfide catalyst;
FIG. 4 is a graph of OER polarization for a cerium doped nickel sulfide catalyst;
FIG. 5 is a graph of the UOR polarization curve for a cerium doped nickel sulfide catalyst;
FIG. 6 is an OER Taphill slope plot for a cerium doped nickel sulfide catalyst;
FIG. 7 is a UOR tafel slope plot of a cerium doped nickel sulfide catalyst;
FIG. 8 is a graph of polarization of a cerium doped nickel sulfide catalyst before and after 1000 cycles of OER;
FIG. 9 is a graph of polarization of a cerium doped nickel sulfide catalyst before and after 1000 cycles of UOR;
FIG. 10 is a graph of OER i-t stability test for cerium doped nickel sulfide catalysts;
FIG. 11 is a graph of UOR i-t stability test for cerium doped nickel sulfide catalysts.
Description of the embodiments
Examples
Pretreatment of a base Carbon Cloth (CC): placing 20 mm multiplied by 20 multiplied by mm multiplied by 0.36 mm carbon in a high-pressure reaction kettle containing 16 mol/L concentrated nitric acid, soaking 12 h at 120 ℃ to clean impurities on the surface of the carbon cloth, taking out, sequentially carrying out ultrasonic treatment in deionized water and absolute ethyl alcohol solution for three times, wherein the ultrasonic treatment time is 15 min each time, and drying 3 h in a 60 ℃ oven to obtain the treated base carbon cloth.
Respectively weighing 0.2908 g nickel nitrate, 0.0868 g cerium nitrate, 0.3 g urea and 0.18 g ammonium fluoride, respectively adding 5 mL deionized water into the four beakers, respectively, placing the magnetons into the beakers at room temperature, magnetically stirring and dissolving for 30 min, pouring the solution in the four beakers into another beakers for mixing, placing the magnetons into the beakers at room temperature, magnetically stirring for 30 min to obtain a mixed solution;
transferring the mixed solution into a high-pressure reaction kettle, simultaneously placing the treated carbon cloth into the kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, heating from room temperature at a heating rate of 3 ℃/min, and performing hydrothermal reaction for a reaction time of 12 h after the reaction temperature reaches 120 ℃ to obtain a crude product of the cerium-doped nickel hydroxide precursor loaded by the carbon cloth;
washing the obtained crude product of the carbon cloth-loaded cerium-doped nickel hydroxide precursor with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying 3 h in a 60 ℃ oven to obtain a dried carbon cloth-loaded cerium-doped nickel hydroxide precursor;
cutting the obtained carbon cloth-loaded cerium-doped nickel hydroxide precursor into a sheet shape with the size of 10 mm multiplied by 20 multiplied by mm multiplied by 0.36 mm, placing the sheet shape at the tail end of a porcelain boat, simultaneously weighing 0.5 sulfur powder g, placing the porcelain boat at the front end of the porcelain boat, placing the porcelain boat into a tubular furnace, introducing nitrogen gas from the upstream position for 20 min, heating from room temperature, wherein the heating rate is 3 ℃/min, after the reaction temperature of the tubular furnace reaches 350 ℃, the heat preservation time is 2 h, performing high-temperature vulcanization reaction, and keeping the reaction process in the nitrogen atmosphere all the time, thus obtaining the cerium-doped nickel sulfide catalyst.
The invention also provides a method for using the cerium doped nickel sulfide catalyst in the oxidation reaction of electrolyzed water and urea.
The performance of oxygen evolution reaction and urea oxidation reaction of the cerium doped nickel sulfide catalyst is tested by using an electrochemical workstation and adopting a standard three-electrode system, and the specific testing method is as follows:
polarization curve (LSV), cyclic Voltammogram (CV) and stability test curve (i-t) were tested in a mixed solution of 1M KOH, 1M KOH and 0.5. 0.5M urea using a CHI 760E electrochemical workstation, respectively, with the carbon rod as counter electrode and Hg/HgO as reference electrode, and in order to eliminate interference, nitrogen was introduced into the electrolyte for 30 min before each experiment to remove dissolved oxygen in the electrolyte, and the sweep rate was set at 5 mV/s. The results are shown in FIG. 4, FIG. 5, and FIGS. 8-11.
The electrocatalytic kinetics of the catalyst was evaluated by tafel slope by plotting the overpotential (η) versus log (j) to give tafel curve. The results are shown in FIG. 6 and FIG. 7.
According to the X-ray diffraction test method, the analysis in FIG. 1 shows that the cerium doped nickel sulfide catalyst precursor obtained by the invention is Ce-Ni (OH) 2 The main phase of the cerium doped nickel sulfide catalyst is Ce-NiS 2 . Scanning electron micrographs (as shown in FIG. 2) show that the morphology of the catalyst is a flower-like lamellar structure. Energy dispersive X-ray lightThe spectrometer imaging (EDX-mapping, as in FIG. 3) shows that Ni, ce and S are uniformly distributed, and the doping amount of Ce element is very small.
FIGS. 4 and 5 are linear sweep voltammetric polarization curves of the product obtained in the examples as catalysts in 1M KOH, 1M KOH and 0.5. 0.5M urea solution, respectively. The graph shows that the cerium doped nickel sulfide catalyst has good electrocatalytic activity, and the catalyst can reach 10 mA/cm only by 1.40V when in anodic electrolysis in 1M KOH solution 2 Is only 1.28V to 10 mA/cm in the case of anodic electrolysis in a mixed solution of 1M KOH and 0.5. 0.5M urea 2 Is used for the current density of the battery. FIGS. 6 and 7 are graphs of the Tafil slope of the products obtained in the examples, showing that the cerium doped nickel sulfide catalyst of the present invention has a lower Tafil slope. Figures 8 and 9 show that the polarization curves before and after 1000 cycles in the two solutions substantially coincide, demonstrating that the catalyst has high electrocatalytic performance and is stable for a long period of time. FIGS. 10 and 11 illustrate the constant current density of the product obtained according to the invention (10 mA/cm) 2 ) Performance stability can be maintained after continuous testing 80 h.

Claims (5)

1. A preparation method and electrochemical application of cerium doped nickel sulfide catalyst are characterized in that: the mass ratio of reactants in the preparation method of the precursor of the cerium doped nickel sulfide catalyst is that nickel nitrate: cerium nitrate: urea: ammonium fluoride=1:0.299:1.032:0.619.
2. A preparation method and electrochemical application of cerium doped nickel sulfide catalyst are characterized in that: the solvent in the preparation method of the precursor of the cerium doped nickel sulfide catalyst is deionized water, the water consumption for dissolving 0.2908 g nickel nitrate is 5 mL, the water consumption for dissolving 0.0868 g cerium nitrate is 5 mL, the water consumption for dissolving 0.3 g urea is 5 mL, and the water consumption for dissolving 0.18 g ammonium fluoride is 5 mL.
3. A preparation method and electrochemical application of cerium doped nickel sulfide catalyst are characterized in that: the reaction conditions in the preparation method of the precursor of the cerium doped nickel sulfide catalyst are as follows: the reaction temperature was 120℃and the reaction time was 12 h.
4. A preparation method and electrochemical application of cerium doped nickel sulfide catalyst are characterized in that: the cerium doped nickel sulfide catalyst prepared by the invention is applied to oxygen evolution reaction of water under the electrocatalytic condition, and can reach 10 mA/cm only by 1.40V when in anodic electrolysis in 1M KOH solution 2 Is used for the current density of the battery.
5. A preparation method and electrochemical application of cerium doped nickel sulfide catalyst are characterized in that: the cerium doped nickel sulfide catalyst prepared by the invention is applied to urea oxidation reaction under the electrocatalytic condition, and can reach 10 mA/cm only by 1.28V when being anodized in a mixed solution of 1M KOH and 0.5M urea 2 Is used for the current density of the battery.
CN202310062261.5A 2023-01-18 2023-01-18 Preparation method of cerium doped nickel sulfide catalyst and electrochemical application thereof Pending CN117265572A (en)

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Application Number Priority Date Filing Date Title
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