CN108435211B - Preparation method of Ce-doped Ni-Fe-Ce ternary sulfide oxygen evolution catalyst - Google Patents
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Abstract
The invention belongs to the technical field of inorganic material synthesis, and particularly relates to a preparation method of a Ce-doped Ni-Fe-Ce ternary sulfide oxygen evolution catalyst. The invention directly uses metal salt Ni (NO)3)2·6H2O、Fe(NO3)3.9H2O and Ce (NO)3)3·6H2And O is taken as a raw material, water is taken as a solvent, and the ternary composite sulfide catalyst can be obtained by adopting a simple two-step method (coprecipitation and hydrothermal method). Any template agent or auxiliary additive is not required to be added in the reaction, and the obtained product is not required to be subjected to calcination annealing treatment and can be directly used as a catalyst. The prepared catalyst material is used for catalyzing water cracking to generate oxygen, not only provides a green, environment-friendly and low-cost method for the development of the oxygen evolution catalytic material which is urgently needed to be solved, but also provides a fuel cellDevelopments have provided an alternative catalyst material.
Description
Technical Field
The invention belongs to the technical field of inorganic material synthesis, and particularly relates to a preparation method of a Ce-doped Ni-Fe-Ce ternary sulfide oxygen evolution catalyst.
Background
In recent years, with the increasing environmental pollution and energy crisis, the development of renewable green energy becomes a hot spot. Hydrogen energy is a new type of green energy, and has attracted more and more attention because of its advantages such as convenient storage, convenient transportation, high efficiency, etc. Similar to the conversion of solar energy into chemical energy under the action of photosynthesis in nature, water cracking can generate a clean hydrogen energy source. The typical water splitting process is mainly divided into two half-reactions of cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). The overpotential loss of the OER process is much higher (typically several times higher) than that of the HER process, which limits large scale electrolysis of water. The development of efficient and stable electro-catalyst to reduce OER overpotential is the key to realize large-scale water electrolysis hydrogen production. At present, the catalyst with good catalytic effect to OER process mainly contains noble metal Ru 1]And Ir, Pt 2]However, the high price of these materials limits their large-scale application, which has also prompted research on some non-noble metal-based electrocatalysts [3]. Transition metal-based oxide or hydroxide catalysts have attracted extensive attention from researchers due to their advantages of low cost, wide raw materials, environmental friendliness, and the like. Ma et al have developed a series of non-noble metal-based catalysts such as metal framework-derived Co3O4/C material, N, O Co-doped C3N4Membranes etc. [4, 5 ]]Meanwhile, the Gao subject group reports binary non-noble metal-based hierarchical hollow micro-cubic NiCo2O4The material has excellent catalytic performance in OER process [6]. In addition, a large number of studies have shown that inexpensive and environmentally friendly Fe-based materialsThe Fe-based material has certain catalytic oxygen evolution property, and the catalytic activity of the binary composite material obtained by doping the Fe-based material is remarkably improved. For example, Dynagen et al studied the catalytic performance of NiFe LDH material in OER process, however, the dual catalyst dynamics and mass transfer effect still need to be improved when it is used as OER process catalyst [7 ]]. Therefore, the present research proposes to solve the deficiencies of single and two-way catalysts by using the concept of multi-component co-catalysis, in order to further improve the performance of Fe-based catalysts. Oxides of Ce (e.g. CeO)2) Due to its ability to be at Ce3+And Ce4+Free conversion between oxidation states and high oxygen storage performance. The metal sulfide and the corresponding metal oxide have similar reaction properties, and in addition, researches show that the metal sulfide often shows more excellent conductive performance of the corresponding metal oxide, so that the designed and synthesized ternary system Ni-Fe-Ce composite sulfide is beneficial to improving the oxygen evolution catalytic performance.
Disclosure of Invention
Aiming at the defects that the price of the existing noble metal catalyst is high, the large-scale application is difficult, and the performance of the single non-noble metal catalyst is poor, the invention provides a preparation method of a Ce-doped Ni-Fe-Ce ternary sulfide oxygen evolution catalyst. The preparation method adopts a multi-component co-catalysis concept to solve the defect of a single catalyst, so as to further meet the requirement of electrolyzed water on the catalyst. Oxides of Ce (e.g. CeO)2) Due to its ability to be at Ce3+And Ce4+Free conversion between oxidation states and high oxygen storage performance. The metal sulfide and the corresponding metal oxide have similar reaction properties, and in addition, researches show that the metal sulfide often shows more excellent conductive performance of the corresponding metal oxide, so that the ternary Ni-Fe-Ce composite sulfide catalyst prepared by doping a certain amount of Ce into the binary system Ni-Fe compound is provided.
The prepared catalyst material is used for catalyzing water cracking to generate oxygen, so that a green, environment-friendly and low-cost method is provided for the development of the oxygen evolution catalytic material which is urgently needed to be solved at present, and an optional catalyst material is provided for the development of fuel cells.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention directly uses metal salt Ni (NO)3)2·6H2O、Fe(NO3)3.9H2O and Ce (NO)3)3·6H2And O is taken as a raw material, water is taken as a solvent, and a simple two-step hydrothermal method is adopted to obtain the ternary complex sulfide catalyst. In the reaction, no template agent or auxiliary additive is needed to be added, and the obtained product can be directly used as a catalyst without calcination annealing treatment.
A preparation method of a Ni-Fe-Ce ternary composite catalyst comprises the following specific preparation steps:
(1) preparing solution and adjusting pH to weigh Ni (NO) in proportion3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2Adding O (the mass ratio is 1: 1.45-1.53: 1.56-1.65) into 100mL of distilled water, enabling the solid (g) to liquid (mL) ratio to be 1: 8-10, stirring until the O is dissolved, then weighing a certain amount of sodium bicarbonate (the amount of the substance is 2-4 times of that of the metal ions), and continuously stirring and dissolving to obtain a clear solution. Then, dilute ammonia water is added dropwise to adjust the pH of the solution to 8.0-8.5.
(2) After the coprecipitation reaction, the solution is placed at 30-40 ℃ and stirred continuously (speed 120 rmp/min) for reaction for 12-24 h.
(3) And (3) separating and purifying the product, taking out the reaction solution, performing suction filtration, sequentially washing with distilled water for multiple times until the washing solution is neutral, finally washing with absolute ethyl alcohol twice to obtain a brown yellow precipitate, then drying in an oven at 40-60 ℃ for 10-12h, and finally grinding the brown yellow precipitate into powder for later use.
(4) The hydrothermal sulfurizing reaction dries the powder in brown yellow and Na twice the amount of transition metal ion material in the powder2S•9H2Mixing O, stirring and dispersing on a magnetic stirrer, dissolving, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h, and then preserving the heat for 10-12h under the conditions of 120-.
(5) And (3) after the product is treated and reacts and is naturally cooled to room temperature, carrying out suction filtration on the reactant, sequentially washing the reactant for multiple times by using distilled water until the washing liquid is neutral, then washing the reactant by using absolute ethyl alcohol to obtain black precipitate, then drying the black precipitate at 40-60 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate into powder to obtain the catalyst.
The invention has the following beneficial effects:
the invention provides a method for preparing Ce-doped Ni-Fe-Ce ternary complex sulfide in a green and high-efficiency manner, which directly uses Ni (NO)3)2·6H2O、Fe(NO3)3.9H2O and Ce (NO)3)3·6H2And (3) taking O as a raw material, and preparing the Ni-Fe-Ce ternary composite sulfide with high purity by adopting a two-step hydrothermal method. The process directly uses water as a reaction solvent, does not need to add any auxiliary agent, can obtain a final product by a simple one-pot hydrothermal method, has a simple process route, is green and environment-friendly, and has low cost, and the obtained product has a good catalytic oxygen production effect.
Drawings
FIG. 1 is a process flow diagram of the product of the present invention
FIG. 2 shows the difference of Ni (NO)3)2•6H2O、Fe(NO3)3•9H2O、Ce(NO3)3•6H2X-ray diffraction pattern of the synthesized Ni-Fe-Ce ternary complex sulfide under the condition of O proportion;
FIG. 3 is a scanning electron microscope picture of the Ni-Fe-Ce ternary complex sulfide at different proportions;
FIG. 4 is a linear voltammetry (LSV) curve of the Ni-Fe-Ce ternary complex sulfide at different proportions;
FIG. 5 is Tafel curve of Ni-Fe-Ce ternary complex sulfide under different proportions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive. Any feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving the same purpose or having similar purposes, i.e. each feature may be represented by a single example of a generic series of equivalent or similar features unless expressly stated otherwise.
Example 1
(molar ratio of Ni, Fe and Ce is 1:1: 1):
(1) preparing solution and adjusting pH to weigh Ni (NO) in proportion3)2•6H2O、Fe(NO3)3•9H2O、Ce(NO3)3•6H2Adding O (the mass ratio is 1: 1.39: 1.49) into 100mL of distilled water (the solid (g) to liquid (mL) ratio is 1: 10), stirring until the solution is dissolved, then weighing a certain amount of sodium bicarbonate (the amount of substances is 2 times of that of metal ions), and continuously stirring and dissolving to obtain a clear solution. Then, dilute ammonia water was added dropwise to adjust the pH of the solution to 8.0.
(2) Coprecipitation reaction then, the solution was left at 35 ℃ and the reaction was continued with stirring for 18 h.
(3) And (3) separating and purifying the product, taking out the reaction solution, performing suction filtration, sequentially washing with distilled water for multiple times until the washing solution is neutral, finally washing with absolute ethyl alcohol twice, then drying in an oven at 60 ℃ for 12h, and finally grinding into powder for later use.
(4) Hydrothermal sulfurizing reaction to obtain the first-step co-precipitated product in the form of dried powder and Na twice as much as the transition metal ion2S•9H2O, stirring, dispersing and dissolving on a magnetic stirrer, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h, and then preserving the temperature at 120 ℃ for 12 h.
(5) And (3) treating the vulcanization product, naturally cooling the reaction product to room temperature, carrying out suction filtration on the reaction product, sequentially washing the reaction product for multiple times by using distilled water until the washing liquid is neutral, then washing the reaction product by using absolute ethyl alcohol to obtain black precipitate, drying the black precipitate at 40 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate to powder to obtain the catalyst.
Electrode preparation 3.0 mg of the material was weighed into a sample tube, and then 350mL of distilled water, 150 mL of isopropanol and 10. mu.L of Nafion solution were sequentially added thereto and shaken up. And (4) taking out the small test tube after ultrasonic dispersion for 2 h. Accurately measuring 50 mu L of catalyst mixed solution by using a liquid transfer gun, dripping the catalyst mixed solution into a region of 1.0 cm multiplied by 1.0 cm of the carbon paper, uniformly spreading a liquid film on the surface of the Carbon Paper (CP), flatly placing the Carbon Paper (CP) in a ventilated place for naturally airing, and marking the modified electrode as Ni-Fe-Ce/CP, wherein the modified electrode is used as a working electrode in subsequent tests.
The electrochemical performance test of the catalytic performance test electrode material is carried out on a CHI660D electrochemical workstation, and a test system is a standard three-electrode system, wherein in the oxygen evolution performance test process, a Ni-Fe-Ce/CP electrode is used as a working electrode, a 2.0 cm multiplied by 2.0 cm graphite sheet is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 1.0 mol/L KOH solution is used as electrolyte.
The XRD result of the product detection result shows that the diffraction peak is narrow, and the product has good crystallinity; the SEM result shows that the nano particles are aggregated into a micro-structure cluster; the LSV curve of the electrochemical test shows that the overpotential of the material is 350mV, and the Tafel slope is 65 mV/dec.
Example 2
(molar ratio of Ni, Fe and Ce 5:3: 1):
(1) preparing solution and adjusting pH to weigh Ni (NO) in proportion3)2•6H2O、Fe(NO3)3•9H2O and Ce (NO)3)3•6H2O (the mass ratio is 1: 0.83: 0.30) is added into 100mL of distilled water, stirred until dissolved, then a certain amount of sodium bicarbonate (the amount of the substance is 2 times of that of the metal ions) is weighed, and stirred to dissolve continuously to obtain a clear solution. Then, dilute ammonia water was added dropwise to adjust the pH of the solution to 8.5.
(2) Coprecipitation reaction then, the solution was left at 30 ℃ and the reaction was continued for 24h with stirring.
(3) And (3) separating and purifying the product, taking out the reaction solution, performing suction filtration, sequentially washing with distilled water for multiple times until the washing solution is neutral, finally washing with absolute ethyl alcohol twice to obtain a brown yellow precipitate, then drying the brown yellow precipitate in an oven at 60 ℃ for 12 hours, and finally grinding into powder for later use.
(4) Hydrothermal sulfurizing reaction to obtain the first-step co-precipitated product in the form of dried powder and Na twice as much as the transition metal ion2S•9H2O, stirring, dispersing and dissolving on a magnetic stirrer, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h, and then preserving the temperature for 10h at 120 ℃.
(5) And (3) treating the vulcanization product, naturally cooling the reaction product to room temperature, carrying out suction filtration on the reaction product, sequentially washing the reaction product for multiple times by using distilled water until the washing liquid is neutral, then washing the reaction product by using absolute ethyl alcohol to obtain black precipitate, drying the black precipitate at 40 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate to powder to obtain the catalyst.
Electrode preparation 3.0 mg of the material was weighed into a sample tube, and then 350mL of distilled water, 150 mL of isopropanol and 10. mu.L of Nafion solution were sequentially added thereto and shaken up. And (4) taking out the small test tube after ultrasonic dispersion for 2 h. Accurately measuring 50 mu L of catalyst mixed solution by using a liquid transfer gun, dripping the catalyst mixed solution into a region of 1.0 cm multiplied by 1.0 cm of the carbon paper, uniformly spreading a liquid film on the surface of the Carbon Paper (CP), flatly placing the Carbon Paper (CP) in a ventilated place for naturally airing, and marking the modified electrode as Ni-Fe-Ce/CP, wherein the modified electrode is used as a working electrode in subsequent tests.
The electrochemical performance test of the catalytic performance test electrode material is carried out on a CHI660D electrochemical workstation, and a test system is a standard three-electrode system, wherein in the oxygen evolution performance test process, a Ni-Fe-Ce/CP electrode is used as a working electrode, a 2.0 cm multiplied by 2.0 cm graphite sheet is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 1.0 mol/L KOH solution is used as electrolyte.
The XRD result of the product detection result shows that the diffraction peak is narrow, and the product has good crystallinity; the SEM result shows that the nano particles are aggregated into a micro-structure cluster; while the outer surface of the cluster continues to grow some small sized nanoparticles. The LSV test showed that the overpotential was 294mV and the Tafel slope was 57.5 mV/dec.
Example 3
(molar ratio of Ni, Fe and Ce is 5:1: 3):
(1) preparing solution and adjusting pH to weigh Ni (NO)3)2•6H2O、Fe(NO3)3•9H2O、Ce(NO3)3•6H2O (mass ratio 1: 0.28: 0.89) is added into 100mL of distilled water, stirred until dissolved, then a certain amount of sodium bicarbonate (the amount of the substance is 2 times of the metal ion) is weighed, and stirring is continued to dissolve to obtain a clear solution. Then, dilute ammonia water was added dropwise to adjust the pH of the solution to 8.5.
(2) Coprecipitation reaction then, the solution was left at 40 ℃ and the reaction was continued for 12h with stirring.
(3) And (3) separating and purifying the product, taking out the reaction solution, performing suction filtration, sequentially washing with distilled water for multiple times until the washing solution is neutral, finally washing with absolute ethyl alcohol twice to obtain a brown yellow precipitate, then drying the brown yellow precipitate in an oven at 60 ℃ for 12 hours, and finally grinding into powder for later use.
(4) Hydrothermal sulfurizing reaction to obtain the first-step co-precipitated product in the form of dried powder and Na twice as much as the transition metal ion2S•9H2O, stirring, dispersing and dissolving on a magnetic stirrer, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h, and then preserving the temperature at 120 ℃ for 12 h.
(5) And (3) treating the vulcanization product, naturally cooling the reaction product to room temperature, carrying out suction filtration on the reaction product, sequentially washing the reaction product for multiple times by using distilled water until the washing liquid is neutral, then washing the reaction product by using absolute ethyl alcohol to obtain black precipitate, then drying the black precipitate at 40 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate to powder to obtain the catalyst for later use.
Electrode preparation 3.0 mg of the material was weighed into a sample tube, and then 350mL of distilled water, 150 mL of isopropanol and 10. mu.L of Nafion solution were sequentially added thereto and shaken up. And (4) taking out the small test tube after ultrasonic dispersion for 2 h. Accurately measuring 50 mu L of catalyst mixed solution by using a liquid transfer gun, dripping the catalyst mixed solution into a region of 1.0 cm multiplied by 1.0 cm of the carbon paper, uniformly spreading a liquid film on the surface of the Carbon Paper (CP), flatly placing the Carbon Paper (CP) in a ventilated place for naturally airing, and marking the modified electrode as Ni-Fe-Ce/CP, wherein the modified electrode is used as a working electrode in subsequent tests.
The electrochemical performance test of the catalytic performance test electrode material is carried out on a CHI660D electrochemical workstation, and a test system is a standard three-electrode system, wherein in the oxygen evolution performance test process, a Ni-Fe-Ce/CP electrode is used as a working electrode, a 2.0 cm multiplied by 2.0 cm graphite sheet is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 1.0 mol/L KOH solution is used as electrolyte.
The XRD result of the product detection result shows that the diffraction peak is narrow, and the product has good crystallinity; the SEM result shows that the nano particles are aggregated into a micro-structure cluster; the LSV test shows that the overpotential is 305mV, and the Tafel slope is 76 mV/dec.
Example 4
(molar ratio of Ni, Fe and Ce is 4:1: 1):
(1) preparing solution and adjusting pH to weigh Ni (NO)3)2•6H2O、Fe(NO3)3•9H2O、Ce(NO3)3•6H2O (the mass ratio is 1: 0.35: 0.37) is added into 100mL of distilled water, stirred until dissolved, then a certain amount of sodium bicarbonate (the amount of the substance is 2 times of that of the metal ions) is weighed, and stirring is continued to dissolve to obtain a clear solution. Then, dilute ammonia water was added dropwise to adjust the pH of the solution to 8.0.
(2) Coprecipitation reaction then, the solution was left at 30 ℃ and the reaction was continued for 24h with stirring.
(3) And (3) separating and purifying the product, taking out the reaction solution, performing suction filtration, sequentially washing with distilled water for multiple times until the washing solution is neutral, finally washing with absolute ethyl alcohol twice to obtain a brown yellow precipitate, then drying the brown yellow precipitate in an oven at 60 ℃ for 12 hours, and finally grinding into powder for later use.
(4) Hydrothermal sulfurizing reaction to obtain the first-step co-precipitated product in the form of dried powder and Na twice as much as the transition metal ion2S•9H2O, stirring, dispersing and dissolving on a magnetic stirrer, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h,then keeping the temperature at 120 ℃ for 12 h.
(5) And (3) treating the vulcanization product, naturally cooling the reaction product to room temperature, carrying out suction filtration on the reaction product, sequentially washing the reaction product for multiple times by using distilled water until the washing liquid is neutral, then washing the reaction product by using absolute ethyl alcohol to obtain black precipitate, drying the black precipitate at 40 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate to powder to obtain the catalyst.
Electrode preparation 3.0 mg of the material was weighed into a sample tube, and then 350mL of distilled water, 150 mL of isopropanol and 10. mu.L of Nafion solution were sequentially added thereto and shaken up. And taking out the small test tube after ultrasonic dispersion for 3 hours. Accurately measuring 50 mu L of catalyst mixed solution by using a liquid transfer gun, dripping the catalyst mixed solution into a region of 1.0 cm multiplied by 1.0 cm of the carbon paper, uniformly spreading a liquid film on the surface of the Carbon Paper (CP), flatly placing the Carbon Paper (CP) in a ventilated place for naturally airing, and marking the modified electrode as Ni-Fe-Ce/CP, wherein the modified electrode is used as a working electrode in subsequent tests.
The electrochemical performance test of the catalytic performance test electrode material is carried out on a CHI660D electrochemical workstation, a test system is a standard three-electrode system, a Ni-Fe-Ce/CP electrode is used as a working electrode, a 2.0 cm multiplied by 2.0 cm graphite sheet is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 1.0 mol/L KOH solution is used as electrolyte in the oxygen evolution performance test.
The XRD result of the product detection result shows that the diffraction peak is narrow, and the product has good crystallinity; the SEM result shows that the nano particles are aggregated to form a microstructure cluster, and the outside of the large microstructure cluster is also partially stacked to form an irregular smaller micro cluster structure. The overpotential of the LSV curve surface is 340mV, and the Tafel slope is 70.7 mV/dec.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. The application of the Ni-Fe-Ce ternary composite catalyst in catalyzing water cracking to produce oxygen is characterized in that the preparation method of the catalyst comprises the following steps:
(1) preparing solution and adjusting pH to weigh Ni (NO) in proportion3)2·6H2O、Fe(NO3)3·9H2O and Ce (NO)3)3·6H2Adding O, adding distilled water, stirring until the solution is dissolved, adding sodium bicarbonate, and continuously stirring for dissolving to obtain a clear solution; then dropwise adding dilute ammonia water to adjust the pH value of the solution to 8.0-8.5; ni (NO)3)2·6H2O、Fe(NO3)3·9H2O and Ce (NO)3)3·6H2The mass ratio of O is 1: 1.45-1.53: 1.56-1.65;
(2) putting the solution in a coprecipitation reaction at 30-40 ℃, and continuously stirring for reaction for 12-24h to obtain a reaction solution;
(3) separating and purifying the product, taking out the reaction solution, performing suction filtration, washing with distilled water for multiple times in sequence until the washing solution is neutral, finally washing with absolute ethyl alcohol twice to obtain a brown yellow precipitate, then placing the brown yellow precipitate in a drying oven at 40-60 ℃ for drying for 10-12h, and finally grinding the brown yellow precipitate into powder for later use;
(4) hydrothermal process sulfurization reaction of brown yellow powder and Na2S•9H2Mixing O, stirring and dispersing and dissolving on a magnetic stirrer, then transferring to a 100mL reaction kettle after ultrasonic treatment for 0.5h, and then preserving heat for 10-12h at the temperature of 120-;
(5) and (3) after the product is treated and reacts and is naturally cooled to room temperature, carrying out suction filtration on the reactant, sequentially washing the reactant for multiple times by using distilled water until the washing liquid is neutral, then washing the reactant by using absolute ethyl alcohol to obtain black precipitate, then drying the black precipitate at 40-60 ℃ until the black precipitate is completely dried, and finally grinding the black precipitate into powder to obtain the catalyst.
2. The use of claim 1, wherein: after the distilled water is added in the step (1), the ratio of the mass g of the solid to the volume mL of the liquid in the solution is 1: 8-10; the addition amount of sodium bicarbonate is 2-4 times of the amount of metal ion substance.
3. The use of claim 1, wherein: the stirring speed in the step (2) is 120-200 rmp/min.
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