CN115161661A - Composite catalyst material and preparation method and application thereof - Google Patents

Composite catalyst material and preparation method and application thereof Download PDF

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CN115161661A
CN115161661A CN202210642293.8A CN202210642293A CN115161661A CN 115161661 A CN115161661 A CN 115161661A CN 202210642293 A CN202210642293 A CN 202210642293A CN 115161661 A CN115161661 A CN 115161661A
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composite catalyst
catalyst material
nickel
transition metal
selenide
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吴慧敏
王荣瑶
孙争光
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Hubei University
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Zhuhai Huda Technology Co ltd
Hubei University
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C—CHEMISTRY; METALLURGY
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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Abstract

The invention provides a composite catalyst material and a preparation method and application thereof. The preparation method of the composite catalyst material comprises the steps of placing a selenide solution in a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction to obtain selenide, namely the composite catalyst material; or respectively putting the sodium hypophosphite and the foamed nickel into a tube furnace, and calcining to obtain Ni 2 P/A NF material; mixing Ni 2 Adding a P/NF material into the selenide solution, and carrying out hydrothermal reaction to obtain a composite catalyst material; the composite catalyst material shows excellent catalytic activity on both the cathodic hydrogen evolution reaction and the anodic urea oxidation reaction of a urea-water electrolysis system; at 100 mA-cm ‑2 In the process, the cell voltage is only 1.607V, which is 232mV lower than that of pure water electrolysis, thus greatly reducing the energy consumption for hydrogen production by electrolysis. The composite catalyst material has application prospects in the aspects of hydrogen production by electrolysis and treatment of urea wastewater.

Description

Composite catalyst material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst materials, in particular to a composite catalyst material and a preparation method and application thereof.
Background
At present, hydrogen energy is considered to be an ideal clean energy source because the combustion heat value is high and the combustion product is water. The method for producing Hydrogen (HER) by electrolyzing water is a high-efficiency, environment-friendly and high-purity hydrogen production method. The development of hydrogen evolution electrocatalysts with lower overpotentials is one of the important means to optimize the process. To date, platinum (Pt) and its alloys have been considered to be an excellent class of catalysts in HER. But the scarcity and high price of Pt greatly limit the application of large-scale commercialization. Therefore, reducing the amount of Pt used or developing a Pt-free catalyst is a more effective way to realize a low-cost catalyst.
At present, researchers change the chemical composition and electronic structure of a non-noble metal catalyst through measures such as alloying, surface modification, hybridization and the like, and design and synthesize a series of non-noble metal catalysts capable of replacing Pt-based noble metals. Among them, the transition metal phosphide catalyst is receiving attention because of having the characteristics of electronic structural properties similar to hydrogenase and noble metal Pt, good conductivity and corrosion resistance. However, the hydrogen evolution activity of the existing phosphide catalyst still cannot be compared with that of the Pt noble metal catalyst.
Based on the defects of the existing hydrogen production catalyst by electrolyzing water, the improvement is needed.
Disclosure of Invention
In view of the above, the present invention provides a composite catalyst material, and a preparation method and an application thereof, so as to solve or partially solve the technical problems in the prior art.
In a first aspect, the present invention provides a method for preparing a composite catalyst material, comprising the steps of:
adding transition metal salt and selenate into a mixed solution consisting of diethylenetriamine and water, stirring, adding hydrazine hydrate, and continuously stirring to obtain a selenide solution;
placing the selenide solution into a reaction kettle, adding foamed nickel into the reaction kettle, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain selenide loaded on the foamed nickel, namely the composite catalyst material;
or respectively placing sodium hypophosphite and foamed nickel in a tubular furnace, heating to 250-350 ℃ under the protection of inert gas, and keeping for 1-3 h to obtain Ni 2 A P/NF material;
mixing Ni 2 Adding the P/NF material into the selenide solution, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain the composite catalyst material.
In a second aspect, the invention also provides a composite catalyst material prepared by the preparation method.
In a third aspect, the invention also provides a composite catalyst material prepared by the preparation method or an application of the composite catalyst material as a catalyst.
Compared with the prior art, the preparation method and the preparation method of the composite catalyst material have the following beneficial effects:
the preparation method of the composite catalyst material comprises the steps of placing a selenide solution in a reaction kettle, adding foamed nickel into the reaction kettle, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain selenide loaded on the foamed nickel, namely the composite catalyst material; or respectively placing sodium hypophosphite and foamed nickel in a tubular furnace, heating to 250-350 ℃ under the protection of inert gas, and keeping for 1-3 h to obtain Ni 2 A P/NF material; mixing Ni 2 Adding the P/NF material into the selenide solution, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain a composite catalyst material; the composite catalyst material prepared by the invention is used for treating the negative ions of a urea-water electrolysis systemThe Hydrogen Evolution Reaction (HER) and the anodic Urea Oxidation Reaction (UOR) both show excellent catalytic activity, and can reach 100 mA-cm in the UOR direction only by 1.383V -2 Much lower than noble metal-based catalysts; double-electrode electrolytic cell Ni constructed based on the method 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 The performance of the same is excellent; at 100 mA-cm -2 In the process, the cell voltage is only 1.607V, which is 232mV lower than that of pure water electrolysis, thus greatly reducing the energy consumption for hydrogen production by electrolysis. In conclusion, the bifunctional electrocatalyst has application prospects in hydrogen production by electrolysis and treatment of urea wastewater.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a comparison of LSV curves of the selenide materials prepared in examples 1-5 in a 1M KOH mixed electrolyte (HER) containing 0.5M urea, respectively;
FIG. 2 is a comparison of LSV curves of selenide materials prepared in examples 6-12 in a 1M KOH mixed electrolyte (HER) containing 0.5M urea, respectively;
FIG. 3 is a comparison of LSV curves of selenide materials prepared in examples 13-15, respectively in a 1M KOH mixed electrolyte (HER) containing 0.5M urea;
FIG. 4 is a comparison graph of Tafel slopes of the respective best selenides of the Fe, co, ni series in examples 1-15;
FIG. 5 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 XRD pattern of/NF;
FIG. 6 shows a composite catalyst material Ni prepared in example 17 2 P/CoSe 2 An X-ray photoelectron spectrum of/NF;
FIG. 7 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 SEM images of/NF at different magnifications;
FIG. 8 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 (iv) transmission electron microscopy images of/NF;
FIG. 9 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 The LSV curves of the/NF in 0.5M pure urea, 1M KOH electrolyte (OER) and 1M KOH mixed electrolyte (UOR) containing 0.5M urea are compared respectively;
FIG. 10 shows a composite catalyst material and IrO prepared in examples 16 to 20 2 LSV curve of NF in 1M KOH mixed electrolyte containing 0.5M urea;
FIG. 11 shows a composite catalyst material and IrO prepared in examples 16 to 20 2 Tafel curves for/NF and NF versus the UOR direction;
FIG. 12 is a line graph of Tafel slope values for each of the samples of FIG. 11;
FIG. 13 shows a composite catalyst material Ni prepared in example 17 2 P/CoSe 2 LSV curves of/NF versus UOR direction at different sweep speeds;
FIG. 14 is a multi-step chronoamperometric curve of composite catalyst materials prepared in examples 16-20;
FIG. 15 is the LSV curve of the composite catalyst materials prepared in examples 16-20, pt/C/NF in 1MKOH electrolyte containing 0.5M urea;
FIG. 16 shows the temperature at 100mA cm -2 The overpotential contrast required for each material of fig. 15;
FIG. 17 is a Tafel plot of Pt/C/NF, NF versus UOR orientation for the composite catalyst materials prepared in examples 16-20;
FIG. 18 shows a composite catalyst material Ni prepared in example 17 2 P/CoSe 2 the/NF vs. UOR direction, LSV curves at different sweep rates;
FIG. 19 is a multi-step chronoamperometric curve of the composite catalyst materials prepared in examples 16-20 in a 1M KOH electrolyte containing 0.5M urea;
FIG. 20 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 Comparing LSV curves before and after NF 2000 circle cyclic voltammetry scanning;
FIG. 21 is a graph showing electrochemical impedance measurements of composite catalyst materials prepared in examples 16 to 20 in a 1M KOH electrolyte containing 0.5M urea;
FIG. 22 shows double-layer capacitances (C) of composite catalyst materials prepared in examples 16 to 20 dl ) A value;
FIG. 23 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 /NF respectively used as anode and cathode, constructed Ni 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 a/NF two-electrode cell schematic;
FIG. 24 is a plot of the polarization of a two-electrode cell constructed of different materials in a 1M KOH electrolyte containing 0.5M urea;
FIG. 25 shows a composite catalyst material Ni prepared in example 17 2 P/CoSe 2 Ni of NF construction 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 Comparing polarization curves of the NF double-electrode electrolytic cell in pure water and electrolyte containing 0.5M urea;
FIG. 26 shows Ni, a composite catalyst material prepared in example 17, at a cell voltage of 1.48V 2 P/CoSe 2 Ni of NF construction 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 Chronoamperometric curves (i-t) of the NF Bipolar electrolyser.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
The embodiment of the application provides a preparation method of a composite catalyst material, which comprises the following steps:
s1, adding a transition metal salt and selenate into a mixed solution composed of diethylenetriamine and water, stirring, adding hydrazine hydrate, and continuously stirring to obtain a selenide solution;
s2, placing the selenide solution in a reaction kettle, adding a load matrix foamed nickel, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain selenide loaded on the foamed nickel, namely the composite catalyst material;
alternatively, the method comprises the following steps:
s3, respectively placing the sodium hypophosphite and the foamed nickel in a tubular furnace, heating to 250-350 ℃ under the protection of inert gas, and keeping for 1-3 hours to obtain Ni 2 A P/NF material;
s4, preparing selenide solution according to the same method in the step S1, and adding Ni 2 Adding a P/NF material serving as a load matrix into a selenide solution, and carrying out hydrothermal reaction for 14-18 h at the temperature of 120-160 ℃ to obtain the composite catalyst material.
The preparation method of the composite catalyst material provided in the embodiment of the present application includes adding transition metal salt and selenate to a mixed solution of Diethylenetriamine (DETA) and water, adding hydrazine hydrate, placing in a reaction kettle, adding nickel foam, and performing a hydrothermal reaction to obtain selenide loaded on the nickel foam, which is the composite catalyst material; or respectively placing sodium hypophosphite and foamed nickel in a tube furnace, and calcining under the protection of inert gas to obtain Ni 2 The P/NF material is characterized in that sodium hypophosphite is arranged in the tubular furnace and located at the upstream of the inert gas flowing direction, foamed nickel is located in the tubular furnace and located at the downstream of the inert gas flowing direction, and the interval between the sodium hypophosphite and the foamed nickel is about 15 cm. Then passing Ni 2 And carrying out hydrothermal reaction on the P/NF material and the selenide solution to obtain the composite catalyst material.
The preparation method of the composite catalyst material takes the foamed nickel as a nickel source and a conductive matrix, takes the sodium hypophosphite as a phosphorus source, and prepares the Ni by a high-temperature calcination method 2 P/NF, followed by solvothermal coupling with selenide CoSe for optimal performance for screening 2 Compounding to obtain Ni grown in situ on foamed nickel 2 P/CoSe 2 . Optimization ofThe amount of phosphorus source added and the calcination temperature were 1.2g NaH at 300 deg.C 2 PO 2 Ni with optimal cellular porous fluffy structure is synthesized 2 P/CoSe 2 and/NF. The catalyst shows excellent catalytic activity on cathodic Hydrogen Evolution Reaction (HER) and anodic Urea Oxidation Reaction (UOR) of a urea-water electrolysis system, and can reach 100 mA-cm in the UOR direction only by 1.383V -2 Much lower than noble metal based catalysts. Double-electrode electrolytic cell Ni based on construction 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 The performance of the/NF is also excellent. At 100 mA-cm -2 In the process, the cell voltage is only 1.607V, which is 232mV lower than that of pure water electrolysis, thus greatly reducing the energy consumption for hydrogen production by electrolysis. In conclusion, the bifunctional electrocatalyst has application prospects in the aspects of hydrogen production by electrolysis and treatment of urea wastewater.
Specifically, the inert gas may be nitrogen or a rare gas.
In some embodiments, the transition metal salt comprises at least one of a transition metal iron salt, a transition metal cobalt salt, a transition metal nickel salt.
In some embodiments, the transition metal ferric salt comprises at least one of ferric nitrate, ferric sulfate, ferric chloride;
the transition metal cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate and cobalt chloride;
the transition metal nickel salt comprises at least one of nickel sulfate, nickel nitrate and nickel chloride.
In some embodiments, the selenate comprises at least one of sodium selenite and potassium selenite.
In some embodiments, the method comprises the steps of adding a transition metal salt and selenate into a mixed solution composed of diethylenetriamine and water, stirring, adding hydrazine hydrate, and then continuously stirring to obtain a selenide solution, wherein the mass-to-volume ratio of the transition metal salt to the selenate to the water to the hydrazine hydrate is (0.2-0.5) g, (0.05-1.5) g, (5-10) mL.
In some embodiments, the mass ratio of the transition metal salt to the selenate to the sodium hypophosphite is (0.2-0.5) g, (0.05-1.5) g, (0.5-1.5) g.
In some embodiments, before placing the foamed nickel in the reaction kettle and before placing the foamed nickel in the tube furnace, the method further comprises sequentially performing ultrasonic cleaning on the foamed nickel by using hydrochloric acid, acetone, ethanol and ultrapure water.
In some embodiments, the nickel foam is added into a reaction kettle, and after the hydrothermal reaction is carried out for 14-18 h at 120-160 ℃, the hydrothermal reaction is sequentially washed by absolute ethyl alcohol and water, and then dried at 50-70 ℃ to obtain the selenide.
Based on the same inventive concept, the embodiment of the application also provides a composite catalyst material prepared by the preparation method.
Based on the same inventive concept, the embodiment of the application also provides the composite catalyst material prepared by the preparation method or the application of the composite catalyst material as a catalyst.
Based on the same inventive concept, the embodiment of the application also provides a composite catalyst material prepared by the preparation method.
Based on the same inventive concept, the embodiment of the application also provides an application of the composite catalyst material as a catalyst.
Specifically, the composite catalyst material can be used as a catalyst for efficiently catalyzing hydrogen production, and can also effectively catalyze the decomposition of urea in wastewater.
The following further describes the preparation method of the composite catalyst material of the present application with specific examples, and this section further illustrates the present invention with reference to the specific examples, but should not be construed as limiting the present invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of a composite catalyst material, which comprises the following steps:
s1, sequentially adopting 3M dilute hydrochloric acid solution and 3M dilute hydrochloric acid solutionCutting the foam nickel (4X 2 cm) with ketone, ethanol and ultrapure water 2 Namely, the length is 4cm, the width is 2 cm) is subjected to ultrasonic cleaning, and vacuum drying is carried out for standby;
s2, adding 0.291g of cobalt nitrate hexahydrate and 0.524g of sodium selenite pentahydrate into a mixed solution consisting of 20mL of diethylenetriamine and 10mL of water, stirring uniformly, and adding 8.5mL of 50wt% N 2 H 4 ·H 2 O, stirring for 30min again to obtain a selenide solution;
and S3, placing the selenide solution into a reaction kettle, adding foamed nickel into the reaction kettle, carrying out hydrothermal reaction for 16h at 140 ℃, washing the reaction product with ethanol and water in sequence after the reaction is finished, and drying at 60 ℃ to obtain the selenide (recorded as Co-Se-66.7%) loaded on the foamed nickel.
Example 2
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as the embodiment 1, and is different from the embodiment 1 in that 0.654g of sodium selenite pentahydrate is added in the step S2, the other process parameters are the same as the embodiment 1, and the selenide obtained by preparation is recorded as Co-Se-71.4%.
Example 3
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.786g of sodium selenite pentahydrate is added in step S2, and other process parameters are the same as those in embodiment 1, so that selenide loaded on foamed nickel is prepared and recorded as Co-Se-75.0%.
Example 4
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as the embodiment 1, and is different from the embodiment 1 in that 0.917g of sodium selenite pentahydrate is added in the step S2, the other technological parameters are the same as those of the embodiment 1, and the selenide loaded on the nickel foam obtained by preparation is recorded as Co-Se-77.8%.
Example 5
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 1.048g of sodium selenite pentahydrate is added in step S2, the rest technological parameters are the same as those in embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Co-Se-80.0%.
Example 6
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as the embodiment 1, and is different from the embodiment 1 in that 0.291g of nickel nitrate hexahydrate is used to replace 0.291g of cobalt nitrate hexahydrate, 0.066g of sodium selenite pentahydrate is used to replace 0.524g of sodium selenite pentahydrate in the step S2, the rest technological parameters are the same as the embodiment 1, and the selenide loaded on the nickel foam is recorded as Ni-Se-20.0%.
Example 7
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as the embodiment 1, and is different from the embodiment 1 in that 0.291g of nickel nitrate hexahydrate is used to replace 0.291g of cobalt nitrate hexahydrate, 0.174g of sodium selenite pentahydrate is used to replace 0.524g of sodium selenite pentahydrate in the step S2, the rest technological parameters are the same as the embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Ni-Se-40.0%.
Example 8
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.291g of nickel nitrate hexahydrate is used instead of 0.291g of cobalt nitrate hexahydrate, 0.242g of sodium selenite pentahydrate is used instead of 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Ni-Se-48.0%.
Example 9
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.291g of nickel nitrate hexahydrate is used instead of 0.291g of cobalt nitrate hexahydrate, 0.284g of sodium selenite pentahydrate is used instead of 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Ni-Se-52.0%.
Example 10
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.291g of nickel nitrate hexahydrate is used for replacing 0.291g of cobalt nitrate hexahydrate, 0.333g of sodium selenite pentahydrate is used for replacing 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the prepared selenide loaded on foamed nickel is recorded as Ni-Se-56.0%.
Example 11
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.291g of nickel nitrate hexahydrate is used instead of 0.291g of cobalt nitrate hexahydrate, 0.557g of sodium selenite pentahydrate is used instead of 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Ni-Se-68.0%.
Example 12
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.291g of nickel nitrate hexahydrate is used instead of 0.291g of cobalt nitrate hexahydrate, 1.048g of sodium selenite pentahydrate is used instead of 0.524g of sodium selenite pentahydrate in step S2, the rest process parameters are the same as those in embodiment 1, and the selenide loaded on the foamed nickel obtained by preparation is recorded as Ni-Se-80.0%.
Example 13
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.404g of ferric nitrate nonahydrate is used instead of 0.291g of cobalt nitrate hexahydrate, 0.283g of sodium selenite pentahydrate is used instead of 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the selenide loaded on the nickel foam is recorded as Fe-Se-52.0%.
Example 14
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.404g of ferric nitrate nonahydrate is used in step S2 to replace 0.291g of cobalt nitrate hexahydrate, the rest of process parameters are the same as those in embodiment 1, and the prepared selenide loaded on foamed nickel is recorded as Fe-Se-66.7%.
Example 15
The embodiment of the application provides a preparation method of a composite catalyst material, which is the same as that in embodiment 1, except that 0.404g of ferric nitrate nonahydrate is used to replace 0.291g of cobalt nitrate hexahydrate, 1.048g of sodium selenite pentahydrate is used to replace 0.524g of sodium selenite pentahydrate in step S2, and the rest technological parameters are the same as those in embodiment 1, and the prepared selenide loaded on foamed nickel is recorded as Fe-Se-80.0%.
Example 16
The embodiment of the application provides a preparation method of a composite catalyst material, which comprises the following steps:
s1, sequentially adopting 3M dilute hydrochloric acid solution, acetone, ethanol and ultrapure water to prepare the cut nickel foam (4 multiplied by 2 cm) 2 Namely, the length is 4cm, the width is 2 cm) is subjected to ultrasonic cleaning, and vacuum drying is carried out for standby;
s2, adding 0.291g of cobalt nitrate hexahydrate and 0.786g of sodium selenite pentahydrate into a mixed solution consisting of 20mL of diethylenetriamine and 10mL of water, stirring uniformly, and adding 8.5mL of 50wt% N 2 H 4 ·H 2 O, stirring for 30min again to obtain a selenide solution;
s3, respectively placing 1.2g of sodium hypophosphite and the foamed nickel treated in the S1 into a tubular furnace, heating to 250 ℃ under the protection of inert gas, and keeping for 2 hours to obtain Ni 2 A P/NF material;
s4, mixing Ni in the step S3 2 Adding a P/NF material serving as a load matrix into a selenide solution in S2, carrying out hydrothermal reaction for 16h at 140 ℃, washing a reaction product with ethanol and water in sequence, and drying at 60 ℃ to obtain a composite catalyst material, wherein the prepared composite catalyst material is marked as Ni 2 P/CoSe 2 /NF-1。
Example 17
The preparation method of the composite catalyst material provided in the embodiment of the present application is the same as that in embodiment 16, except that the calcination temperature in step S3 is 300 ℃, the remaining process parameters are the same as those in embodiment 16, and the composite catalyst material obtained by the preparation is denoted as Ni 2 P/CoSe 2 /NF。
Example 18
The preparation method of the composite catalyst material provided in the embodiment of the present application is the same as that in embodiment 16, except that the calcination temperature in step S3 is 350 ℃, the remaining process parameters are the same as those in embodiment 16, and the prepared composite catalyst material is denoted as Ni 2 P/CoSe 2 /NF-3。
Example 19
The preparation method of the composite catalyst material provided in the embodiment of the present application is the same as that in embodiment 16, except that step S3 specifically includes: respectively placing 0.8g of sodium hypophosphite and foamed nickel in a tube furnace, heating to 300 ℃ under the protection of inert gas, and keeping for 2 hours to obtain Ni 2 A P/NF material; the rest of the process parameters are the same as those in example 16, and the prepared composite catalyst material is recorded as Ni 2 P/CoSe 2 /NF-4。
Example 20
The preparation method of the composite catalyst material provided in the embodiment of the present application is the same as that in embodiment 16, except that step S3 specifically includes: respectively placing 1.6g of sodium hypophosphite and foamed nickel in a tube furnace, heating to 300 ℃ under the protection of inert gas, and keeping for 2 hours to obtain Ni 2 A P/NF material; the rest of the process parameters are the same as those in example 16, and the prepared composite catalyst material is recorded as Ni 2 P/CoSe 2 /NF-5。
Performance testing
LSV curves of the selenides in a 1M KOH mixed electrolyte containing 0.5M urea were respectively tested at a scan rate of 5mV/s using the selenides supported on nickel foam prepared in examples 1-15 as a working electrode, an Hg/HgO electrode as a reference electrode, and a carbon rod as a counter electrode, and the results are shown in FIGS. 1-3.
FIG. 4 is a comparison of Tafel slopes for the best selenides of the Fe, co, ni series of examples 1-15. As can be seen from FIG. 4, co-Se-75% (corresponding to example 3) has the lowest Tafel slope, indicating that it has the fastest electron transfer rate. Therefore, the selenide solution selected in example 3 was used as the optimal selenide solution.
FIG. 5 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 /NF and CoSe 2 、Ni 2 XRD patterns of P and Ni. As can be seen from FIG. 5, ni 2 P/CoSe 2 the/NF was synthesized successfully.
FIG. 6 shows a composite catalyst material N prepared in example 17i 2 P/CoSe 2 The X-ray photoelectron spectrum (XPS) of/NF, the graphs (a) Ni 2P, (b) P2P, (c) Co 2P, and (d) Se 3d are the corresponding high resolution peak separation spectra. As can be seen from FIG. 6, ni is present in the composite catalyst material at the same time 2 P and CoSe 2 。
FIG. 7 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 (ii)/Scanning Electron Microscope (SEM) images of NF at different magnifications; as is apparent from fig. 7, the nanosheets and the nanowires are interwoven, the material has a honeycomb-shaped porous structure, and the composite catalyst material prepared in example 17 is a honeycomb-shaped porous composite material.
FIG. 8 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 Transmission electron microscopy of/NF (TEM image from FIG. 8, it can be seen that the nanoflakes and nanowires are uniformly interwoven and intimately associated.
FIG. 9 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 The LSV curves of the working electrode of/NF, the reference electrode of Hg/HgO and the counter electrode of carbon rod in 0.5M pure urea, 1M KOH electrolyte (OER) and 1M KOH mixed electrolyte (UOR) containing 0.5M urea were compared at a scanning rate of 5 mV/s.
It is evident from fig. 9 that substantially no electrolysis of pure urea occurs, and that the UOR reaction with urea addition is much lower than the voltage required for OER reaction in pure water, indicating that urea addition is effective in lowering the anodic oxidation potential.
FIG. 10 shows a composite catalyst material and IrO prepared in examples 16 to 20 2 /NF (IrO from 5.0mg, mcMill) 2 (20 wt%) powder, 200. Mu.L of isopropanol, 32. Mu.L of naphthol, and 768. Mu.L of deionized water were mixed well, and 200. Mu.L of the mixture was added dropwise to foamed nickel (0.5 cm. Times.0.5 cm)) as a working electrode, and an Hg/HgO electrode as a reference electrode, a carbon rod as a counter electrode, and an LSV curve in a 1M KOH mixed electrolyte containing 0.5M urea at a scanning rate of 5 mV/s.
As can be seen from FIG. 10, ni is present at the same current density 2 P/CoSe 2 Catalytic voltage of/NFLow, indicating that it has the best catalytic performance.
FIG. 11 shows a composite catalyst material and IrO prepared in examples 16 to 20 2 Tafel curves of/NF and NF in UOR direction (the test method is a three-electrode system, composite catalyst material and IrO) 2 /NF and NF as working electrodes, hg/HgO electrode as reference electrode, carbon rod as counter electrode, at a scan rate of 5 mV/s). FIG. 12 is a line graph of the Tafel slope values for each of the samples in FIG. 11. From FIGS. 11 to 12, ni is clearly shown 2 P/CoSe 2 the/NF has the lowest Tafel slope, which shows the fastest catalytic kinetics and the highest charge transfer efficiency.
FIG. 13 shows a composite catalyst material Ni prepared in example 17 2 P/CoSe 2 LSV curves for the UOR direction at different sweep speeds for/NF (test method same as for the three-electrode system). The inset in FIG. 13 shows that the scan rate has a good positive correlation with current density, indicating that Ni 2 P/CoSe 2 the/NF has good charge mass transfer efficiency.
FIG. 14 is a multi-step chronoamperometric curve of the composite catalyst materials prepared in examples 16 to 20. It can be seen from FIG. 14 that as the voltage step increases, the current all responds rapidly and remains stable rapidly, and Ni 2 P/CoSe 2 The most obvious change of/NF shows that the electronic response is the most sensitive and the mass transfer performance is the most stable.
FIG. 15 is an LSV curve of the composite catalyst materials prepared in examples 16-20, pt/C/NF (prepared by uniformly mixing 5.0mg of Pt/C (20 wt%) powder available from Michelin, 200. Mu.L of isopropanol, 32. Mu.L of naphthol, and 768. Mu.L of deionized water, and then dropping 200. Mu.L of the mixture onto foamed nickel (0.5 cm. Times.0.5 cm)) in a 1M KOH electrolyte containing 0.5M urea (the test method was the same as for the three-electrode system described above). FIG. 16 shows the temperature at 100mA cm -2 The desired overpotential contrast for each material of fig. 15. As can be seen from FIGS. 15 to 16, ni 2 P/CoSe 2 the/NF is closest to the overpotential of noble metal Pt/C/NF, and the performance is the best in preparing materials.
FIG. 17 shows the composite catalyst materials prepared in examples 16-20, pt/C/NF (available from 5.0mg from Meclin corporation)Pt/C (20 wt%) powder, 200. Mu.L isopropanol, 32. Mu.L naphthol and 768. Mu.L deionized water are mixed uniformly, 200. Mu.L of the mixture is dropped on foamed nickel (0.5 cm. Times.0.5 cm) to obtain Tafel curve of NF (foamed nickel) to UOR direction (the test method is the same as the above three-electrode system). From FIG. 17, ni can be seen 2 P/CoSe 2 the/NF has faster catalytic kinetics.
FIG. 18 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 the/NF vs. the UOR direction, LSV curves at different sweep rates (test method same as above for the three-electrode system). The good linear relationship in FIG. 18 indicates Ni 2 P/CoSe 2 the/NF has excellent mass transfer efficiency.
FIG. 19 is a multi-step chronoamperometric curve of the composite catalyst materials prepared in examples 16-20 in a 1M KOH electrolyte containing 0.5M urea. Comparison of FIG. 19 shows that Ni 2 P/CoSe 2 the/NF has stable mass transfer performance.
FIG. 20 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 Ni before and after NF 2000 circle cyclic voltammetry scan (the test method is the same as the three-electrode system) 2 P/CoSe 2 LSV curve of/NF was compared. As can be seen in FIG. 20, the curves before and after 2000 cyclic voltammetry scans substantially coincide, indicating Ni 2 P/CoSe 2 the/NF has excellent electrochemical stability.
FIG. 21 is a graph showing electrochemical impedance measurements of composite catalyst materials prepared in examples 16 to 20 in a 1M KOH electrolyte containing 0.5M urea. From FIG. 21, ni can be seen 2 P/CoSe 2 The fitted semi-circle diameter of/NF is the smallest, indicating that its electrochemical impedance is the smallest and electron transport is faster.
FIG. 22 shows double-layer capacitances (C) of composite catalyst materials prepared in examples 16 to 20 dl ) Value, relative electrochemically active surface area of material and C dl The values are proportional, ni is seen in FIG. 22 2 P/CoSe 2 /NF having the largest C dl The value indicates that it has the greatest telephone line active area.
FIG. 23 shows a composite catalyst prepared in example 17Material Ni 2 P/CoSe 2 /NF respectively used as anode and cathode, constructed Ni 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 a/NF two-electrode electrolyzer, which simultaneously performs a cathodic Hydrogen Evolution Reaction (HER) and an anodic Urea Oxidation Reaction (UOR).
Respectively using the composite catalyst materials prepared in 16-20 as an anode and a cathode according to the method; at the same time, pt/C/NF, irO 2 the/NF is respectively used as an anode and a cathode to construct the Pt/C/NF I IrO of the double-electrode electrolytic cell 2 and/NF. FIG. 24 is a plot of the polarization of a two-electrode cell constructed of the different materials described above in a 1M KOH electrolyte containing 0.5M urea (test method same as for the three-electrode system described above). As can be seen from FIG. 24, ni 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 the/NF has the lowest catalytic voltage and excellent performance.
FIG. 25 shows Ni, a composite catalyst material prepared in example 17 2 P/CoSe 2 Ni of NF construction 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 The polarization curves of the/NF two-electrode cell in pure water and in an electrolyte containing 0.5M urea were compared. It can be seen from fig. 25 that the oxidation potential is effectively lowered at the addition of urea.
FIG. 26 shows Ni, a composite catalyst material prepared in example 18, at a cell voltage of 1.48V 2 P/CoSe 2 Ni of NF construction 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 Chronoamperometric curves (i-t) for a/NF two-electrode cell.
FIG. 26 is a graph showing Ni after a long time operation 2 P/CoSe 2 /NF||Ni 2 P/CoSe 2 The LSV curve of the/NF electrode was compared to the initial LSV curve. Obviously, the current density is slightly reduced after long-term operation, but the whole is stable, which shows that the electrochemical stability is good.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a composite catalyst material is characterized by comprising the following steps:
adding transition metal salt and selenate into a mixed solution consisting of diethylenetriamine and water, stirring, adding hydrazine hydrate, and continuously stirring to obtain a selenide solution;
placing the selenide solution into a reaction kettle, adding foamed nickel into the reaction kettle, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain selenide loaded on the foamed nickel, namely the composite catalyst material;
or respectively placing sodium hypophosphite and foamed nickel in a tube furnace, heating to 250-350 ℃ under the protection of inert gas, and keeping for 1-3 hours to obtain Ni 2 A P/NF material;
mix Ni 2 Adding the P/NF material into the selenide solution, and carrying out hydrothermal reaction for 14-18 h at 120-160 ℃ to obtain the composite catalyst material.
2. The method of preparing the composite catalyst material of claim 1, wherein the transition metal salt comprises at least one of a transition metal iron salt, a transition metal cobalt salt, and a transition metal nickel salt.
3. The method of preparing the composite catalyst material of claim 2, wherein the transition metal ferric salt comprises at least one of ferric nitrate, ferric sulfate, ferric chloride;
the transition metal cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate and cobalt chloride;
the transition metal nickel salt comprises at least one of nickel sulfate, nickel nitrate and nickel chloride.
4. The method for preparing a composite catalyst material according to claim 1, wherein the selenate comprises at least one of sodium selenite and potassium selenite.
5. The preparation method of the composite catalyst material of claim 1, wherein in the step of adding the transition metal salt and the selenate into a mixed solution of diethylenetriamine and water, stirring, adding the hydrazine hydrate, and then continuing stirring to obtain the selenide solution, the mass-to-volume ratio of the transition metal salt, the selenate, the diethylenetriamine, the water and the hydrazine hydrate is (0.2-0.5) g, (0.05-1.5) g, (15-25) mL, (5-10) mL.
6. The method for preparing the composite catalyst material according to claim 5, wherein the mass ratio of the transition metal salt to the selenate to the sodium hypophosphite is (0.2-0.5) g, (0.05-1.5) g, (0.5-1.5) g.
7. The method of preparing the composite catalyst material of claim 1, wherein the step of ultrasonically cleaning the nickel foam sequentially with hydrochloric acid, acetone, ethanol, and water is further included before placing the nickel foam in the reaction vessel and before placing the nickel foam in the tube furnace.
8. The method for preparing the composite catalyst material according to claim 1, wherein the nickel foam is added into a reaction kettle, and after hydrothermal reaction is carried out for 14-18 h at 120-160 ℃, the product of the hydrothermal reaction is washed with absolute ethyl alcohol and water in sequence, and then dried at 50-70 ℃ to obtain the selenide loaded on the nickel foam.
9. A composite catalyst material prepared by the method of any one of claims 1 to 8.
10. Use of a composite catalyst material prepared by the preparation method according to any one of claims 1 to 8 or a composite catalyst material according to claim 9 as a catalyst.
CN202210642293.8A 2022-06-08 2022-06-08 Composite catalyst material and preparation method and application thereof Pending CN115161661A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116443820A (en) * 2023-03-13 2023-07-18 青岛科技大学 Amorphous cobalt selenide nano catalyst and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116443820A (en) * 2023-03-13 2023-07-18 青岛科技大学 Amorphous cobalt selenide nano catalyst and preparation method and application thereof
CN116443820B (en) * 2023-03-13 2024-04-26 青岛科技大学 Amorphous cobalt selenide nano catalyst and preparation method and application thereof

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