CN110560067B - Preparation method and application of iron-nickel alloy catalyst with multi-stage layered structure - Google Patents
Preparation method and application of iron-nickel alloy catalyst with multi-stage layered structure Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 229910052759 nickel Inorganic materials 0.000 claims abstract description 70
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002135 nanosheet Substances 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 33
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 30
- 239000000956 alloy Substances 0.000 claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 24
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- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
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- 229910052742 iron Inorganic materials 0.000 claims description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
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- 229910002555 FeNi Inorganic materials 0.000 abstract description 8
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 9
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
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- 239000002131 composite material Substances 0.000 description 4
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A preparation method and application of a multi-level layered structure iron-nickel alloy catalyst are disclosed, wherein a proper amount of citric acid is used as a chelating agent, an excessive metal salt solution is combined, and a high-dispersion monolithic FeNi alloy catalyst with a foamed nickel load size of 5-12 nm is prepared through a hydrothermal process and subsequent calcination-reduction steps. The bottom layer of the catalyst is a nano-sheet array which grows in a staggered mode, the top layer of the catalyst is spherical nano-particles formed by self-assembly, a developed pore structure of the catalyst is endowed, the subsequent surface catalytic reaction is enhanced, the resistivity of the foamed nickel matrix is improved, and the catalyst can be used for an electrothermal catalytic process. The layered multi-level structure morphology of the catalyst overcomes the defects that the traditional supported catalyst is easy to fall off from the surface of the carrier, has poor dispersion degree and is easy to agglomerate active particles, and widens the application range of the foamed nickel material in the field of electrothermal catalysis.
Description
Technical Field
The invention relates to a preparation method and application of a multi-stage layered structure iron-nickel alloy catalyst.
Background
Nowadays, human production activities emit CO at will2Greenhouse gases bring about numerous environmental problems, and thus the green and sustainable development of economy is severely restricted. In the treatment of CO in a plurality of ways2In the technical scheme, CO2Hydrogenation for preparing CH4The reaction can be carried out under normal pressure (CO)2+4H2→CH4+2H2O,ΔG298130.8kJ/mol), is also the most direct technical approach for realizing efficient circulation of carbon resources, and has received extensive research attention. However, the high operation temperature (250-450 ℃) of methanation reaction and the hot spot generated in the local strong exothermic process are very easy to deposit carbon on the surface of the catalyst or sinter the traditional Ni active particles, which leads to irreversible inactivation of the catalyst ((F.Song, et al. int.J.Hydrogen Energy,2017,42, 4174-4183). based on this, the development of a novel catalytic technical route and the design of a novel structure and a special morphology of the nano catalyst gradually become the current CO2Hot spot direction in hydrogenation field.
Hydrotalcite (LDHs) shows excellent catalytic activity due to its composition adjustability, lattice positioning effect (high dispersion) and intrinsic basicity. In particular, monolithic catalysts prepared by calcining hydrotalcite precursors loaded on porous Nickel Foam (NF) have attracted great research interest in the field of heterogeneous catalysis due to their high thermal conductivity and excellent mass transfer capacity (y.k.li, et al.aiche Journal,2015,61, 4323-. Inevitably, however, uneven heating of the catalyst bed in exothermic catalytic reactions results in a large portion of the catalyst being used with reduced efficiency, agglomeration deactivation and high energy consumption during the reaction. Has a referenceHere, Mortens et al, Chorkendorff, Denmark university of science and technology, and Denmark TopuSol, in 2019, propose a solution for electrically heating a FeCrAl metal tube reactor (S.T.Wismann, et al. science,2019,364, 756-K759) with CH4Steam reforming to produce H2For example, the heating source is in direct close contact with the Ni catalytic sites during the reaction, which can greatly improve the uniformity of heating. However, since the nickel foam has high conductivity, the conventional LDHs loading method (solvothermal method or electrodeposition) does not substantially increase the resistivity of the whole material although many methods are reported, and thus the method is still frequently used for supercapacitors or related electrode materials. Such as Huang, et al. The Chinese patent of invention: CN 108193227A constructs a nickel-iron hydrotalcite composite structure film on a foamed nickel substrate by an in-situ electrodeposition method, can be used for an electrocatalytic oxygen evolution electrode, and shows excellent electrocatalytic activity. Fan, etc. The invention has the following patent: CN 108554413A prepares the three-dimensional multi-level structure nickel-based electro-catalytic material through a hydrothermal method and a subsequent calcination process, and shows excellent electro-catalytic oxygen evolution activity. The surface resistivity of the foam nickel composite material is closely related to the composition, morphology and particle size of a loaded material, however, the current preparation method causes the foam nickel-based composite material to still have high conductivity and is difficult to be used in the resistance thermal catalytic reaction driven by full electricity, and therefore, the resistance thermal application based on the hydrotalcite/foam nickel system derived catalyst is not reported in relevant researches.
Disclosure of Invention
The invention aims to provide a preparation method of a multi-stage layered structure iron-nickel alloy catalyst and application of the catalyst in the field of electro-thermal catalysis. The preparation method is simple and convenient in preparation process, is suitable for batch production, and can avoid the use of a large amount of organic reagents.
The active phase in the multi-stage layered morphology iron-nickel alloy catalyst prepared by the invention is FeNi alloy particles with small size and high dispersion, and the current monolithic catalyst greatly improves the self resistivity of foam Nickel (NF) after crystal grain growth and layered nucleation, can be conveniently used for an electro-thermal catalysis process, and simultaneously shows excellent CO catalysis2Manufacture of CH4And (4) activity.
The method directly adopts conventional urea as a precipitator, simultaneously uses a proper amount of citric acid as a chelating agent, prepares a hydrotalcite (LDHs)/foamed nickel precursor with a multi-stage layered morphology through a simple and green hydrothermal process, and calcines the hydrotalcite (LDHs)/foamed nickel precursor at a slow heating rate in a reducing atmosphere to obtain the multi-stage layered iron-nickel alloy catalyst, wherein FeNi alloy particles are kept highly dispersed and ultra-small in size based on the lattice confinement effect of the hydrotalcite (LDHs). Meanwhile, the monolithic catalyst prepared by the invention shows a developed pore structure, and is beneficial to enhancing the surface catalytic reaction. In particular, based on the layered morphology of the catalyst, compared with the traditional foamed nickel, the resistivity of the obtained monolithic catalyst is obviously increased, and the monolithic catalyst can be used as a monolithic resistor and can perform self-heating through externally applied current, so that the invention can be used in resistance thermocatalytic reaction. Compared with the existing electrothermal catalyst, the catalyst prepared by the invention has the advantages that the proportion of the active center Fe and the active center Ni is adjustable, and the characteristics of small size and high dispersion are kept. Meanwhile, the nano layer is stably attached to the foamed nickel metal substrate due to the strong bonding effect among the nano particles in the crystallization process, and the powder is not easy to fall off or fall off in the reaction process, so that the integral electrothermal alloy type catalyst with stable current structure and morphology is obtained.
The precursor of the multi-stage layered FeNi alloy catalyst is expressed as NiFeAl-LDHs/NF, and is characterized in that LDHs nanosheets are ordered and grow on a foamed nickel substrate in a layered manner, wherein the LDHs nanosheets at the bottom layer are staggered with one another to form a nanosheet array, the diameter of the nanosheets is 50-100 nm, and the thickness of the nanosheets is 5-10 nm; the top LDHs nanosheets are mutually self-assembled into a spherical shape, the diameter of the nanosheets is 100-300 nm, the thickness of the nanosheets is 8-12 nm, and the nanosheets are in close contact with the bottom nanosheet array, so that the precursor presents a special layered three-dimensional multilevel structural shape. And (2) moderately roasting the precursor, wherein the obtained alloy catalyst still maintains the morphological characteristics, the catalyst is NiFeAl/NF, has developed pores and high specific surface area, and all Fe and Ni form small-size alloy particles with the size of 5-10 nm. The obtained alloy catalyst needs to be integrally used as a resistor device, and Joule heat is directly generated by an external proper electric field to act on FeNi alloy particles to drive the heterogeneous catalytic reaction.
The preparation method of the iron-nickel alloy catalyst with the multi-stage layered structure comprises the following steps:
(1) taking a high-porosity foamed nickel metal substrate as a conductive support framework, respectively placing the conductive support framework in a hydrochloric acid solution, deionized water and absolute ethyl alcohol for ultrasonic treatment, and drying in a vacuum drying oven for 6 hours to obtain a foamed nickel substrate without an oxide layer on the surface;
(2) dissolving metal salt, urea and citric acid in deionized water at the same time, transferring the solution into a 100ml polytetrafluoroethylene lining, putting the foamed nickel metal substrate in the step (1), sealing the foamed nickel metal substrate, putting the sealed foamed nickel metal substrate in a stainless steel kettle for screwing, putting the sealed foamed nickel metal substrate in a forced air drying box for hydrothermal reaction, standing the sealed foamed nickel metal substrate at room temperature after the reaction is finished, washing the obtained product with the deionized water until the pH value is 7, and drying the product to obtain a LDHs/foamed nickel precursor with a multi-level layered structure;
(3) the precursor obtained in the step (2) is put in H2Roasting in a reducing atmosphere to obtain a corresponding multistage layered iron-nickel alloy catalyst;
the high-porosity foamed nickel metal substrate in the step (1) is 50-100 mm long, 4-6 mm wide, 1-1.5 mm thick and long: the width is not less than 10:1, the porosity is higher than 95%, the concentration of hydrochloric acid is 3-6 mol/L, the ultrasonic power is 300W, and the ultrasonic time is controlled to be 0.25-0.5 h.
In the step (2), the metal salt comprises divalent Ni2+And trivalent Fe3+Trivalent Al3+A metal salt in the form of nitrate or chloride or their mixture, Ni2+And Fe3+、Al3+Is fixed at a molar ratio of [ Ni ]2+]/[Fe3++Al3+]3: 1, preferably [ Fe ]3+]/[Al3+]0.33 to 1, preferably [ urea ]]/[Ni2++Fe3++Al3+]The amount of [ urea ] is preferably 3.33 to 4]/[ citric acid ]]5-10. The metal salt and urea are in large excess relative to the nickel metal base foam, every 1mmol of bivalent Ni2+Corresponding to 10mg of a foamed nickel metal substrate. The hydrothermal temperature is selected to be 110-140 ℃, the time is 8-12 h, the room-temperature standing time is 12h, and the drying condition is the same as that of the step (1), so that the hierarchical LDHs/foam nickel precursor Ni with the multilevel structure is obtained3FexAly-LDHs/NF。
In the step (3), the roasting conditions are as follows: introduction of H2Roasting the/Ar mixed gas at 500-600 ℃, heating up at a rate of 1-2 ℃/min for 3h to obtain the multi-stage layered Fe-Ni alloy catalyst Ni3FexAly/NF。
And (4) connecting two ends of the modular multistage layered iron-nickel alloy catalyst obtained in the step (3) into a circuit through a pure copper wire, and loading current to generate Joule heat to drive catalytic reaction. The current can be direct current or alternating current, the current loading range is 0A-6A, the voltage loading range is 0V-30V, and the heat production temperature of the catalyst is optimized to be 150-400 ℃.
The preparation process and the principle of the invention are as follows: in the starting solution, the pH of the solution is brought about by the presence of large amounts of metal nitrates<7, the citric acid generates primary and secondary ionization under the acidic condition and is mixed with Fe in the solution3+、Ni2+、Al3+Metal ions are coordinated, so that the metal ions in the solution are captured and gathered around the foam nickel supporting framework; then urea is used as a precipitator, and NH is generated by gradual decomposition in the heating process3Precipitating the metal ions in the solution to form hydroxide species thereof; at this time, due to the presence of the nickel foam matrix, heterogeneous nucleation of metal ions occurs at the surface thereof based on its porous structure and rough dielectric surface, forming starting crystallites. The existence of citric acid can obviously inhibit the homogeneous nucleation process of metal ions and promote the precipitation nucleation of the metal ions on a supporting framework, and particularly, in the preparation method, after the excessive salt solution forms a primary array on the surface of a foamed nickel matrix, the nucleation continues on the surface of the array, the self-assembly forms a spherical morphology stacked by nano sheets, and strong interaction force exists between the nano layers. During calcination-reduction, by a very slow rate of temperature rise: 1-2 ℃/min, continuously maintaining the multi-stage morphology, simultaneously overflowing Ni and Fe from the LDHs laminate, and H2And fusing at high temperature in the atmosphere to form small-size alloy particles, and highly dispersing the obtained alloy particles based on the lattice positioning effect of LDHs to obtain the multistage layered iron-nickel alloy catalyst.Due to the layered structure of the catalyst prepared by the method, the catalyst keeps higher resistivity and can be directly loaded with current to carry out fully electrically driven electro-thermal catalytic reaction.
Compared with the prior art, the invention has the following advantages and characteristics:
(1) the preparation method of the multistage layered FeNi alloy catalyst provided by the invention is not reported in documents, and particularly, the multistage layered FeNi alloy catalyst is obtained by adopting an excess salt solution method for the first time, taking urea as a precipitator and a proper amount of citric acid as a chelating agent through a green hydrothermal method and a subsequent calcination-reduction process.
(2) The NiFeAl/NF prepared by the invention has a unique multistage layered morphology, the bottom layer is a nanosheet array, the diameter of the nanosheet is 50-100 nm, the thickness of the nanosheet is 5-10 nm, the top layer is a self-assembled spherical particle, the particle size is 100-300 nm, Fe and Ni elements separated out from the laminate directly form a bimetal alloy, the small-size and high-dispersion characteristics are kept, and the size of the spherical particle is 5-10 nm.
(3) In the electro-thermal catalysis application, the multi-level structure layered catalyst shows obviously improved resistivity, so that the current can be directly loaded to fully electrically drive and catalyze CO2Hydrogenation breaks through the cognition that the foamed nickel can only be used as a high-conductivity electrode material. The performance test result shows that the catalytic activity of the current FeNi alloy catalyst is improved by 50 percent compared with that of a single Ni particle, the defects of easy falling, low load capacity and easy agglomeration at high temperature of the foam nickel supported catalyst prepared by the traditional method are technically overcome, and the application of the hydrotalcite/foam nickel composite material derived catalyst in the electro-thermal catalysis field is widened.
The preparation method can be used in the field of electro-thermal catalysis.
Drawings
FIG. 1 is a photograph of a real object of LDHs/NF and the catalyst obtained after calcination-reduction; FIG. 1a is a schematic representation of a treated nickel foam; FIG. 1b shows Ni in example 13Fe0.5Al0.5-LDHs/NF; FIG. 1c shows Ni in example 13Fe0.5Al0.5/NF; FIG. 1d shows Ni in example 23Fe0.25Al0.75/NF; FIG. 1e shows Ni in example 33Fe0.33Al0.66/NF；
FIG. 2 is an SEM electron micrograph of treated nickel foam of examples 1-3;
FIG. 3 is the multi-stage layered Fe-Ni hydrotalcite/Ni foam precursor Ni of example 13Fe0.5Al0.5SEM micrograph of LDHs/NF;
FIG. 4 shows the multi-stage layered Fe-Ni alloy catalyst Ni of example 13Fe0.5Al0.5SEM image of/NF bottom layer nano sheet array;
FIG. 5 is the multi-stage layered Fe-Ni alloy catalyst Ni of example 13Fe0.5Al0.5SEM image of/NF top layer rosette particles;
FIG. 6 is the multi-stage layered Fe-Ni alloy catalyst Ni of example 23Fe0.25Al0.75SEM picture of/NF;
FIG. 7 shows the multi-stage layered Fe-Ni alloy catalyst Ni of example 33Fe0.33Al0.66SEM picture of/NF;
FIG. 8 is the multi-stage layered Fe-Ni alloy catalyst Ni of example 33Fe0.33Al0.66STEM element distribution line scanning diagram of/NF;
FIG. 9 is the multi-stage layered Fe-Ni alloy catalyst Ni of example 33Fe0.33Al0.66/NF and Ni alone3Al1Electro-thermocatalytic CO/NF2And (5) comparing hydrogenation activities.
Detailed Description
Example 1:
step 1: cutting the porous foam nickel into pieces with the length of 70mm, the width of 4mm and the thickness of 1.5mm, and placing the pieces in 3mol/L hydrochloric acid for ultrasonic treatment for 0.5h, wherein the ultrasonic power is 300W. And then continuing to perform ultrasonic treatment in deionized water and absolute ethyl alcohol for 0.5h respectively, and drying in a vacuum drying oven for 6h to obtain the foamed nickel metal substrate without the oxide layer on the surface. As shown in fig. 2, nickel foam alone exhibits high porosity characteristics, with the nickel metal skeleton interconnected to form staggered pores;
and 2, step: preferably [ Fe ]3+]/[Al3+]0.009mol Ni (NO) 0.33-13)2·6H2O、0.0015mol Fe(NO3)3·9H2O、0.0015mol Al(NO3)3·9H2Dissolving O, 0.04mol of urea and 0.004mol of citric acid in deionized water, transferring the solution into a 100ml polytetrafluoroethylene lining kettle, putting the foam nickel metal substrate 1 sheet obtained in the step (1) into the reaction kettle, sealing a reaction kettle cover, putting the reaction kettle cover into a stainless steel kettle skin, screwing the reaction kettle cover, putting the reaction kettle into a 110 ℃ blast drying box for hydrothermal reaction for 12 hours, standing the reaction kettle at room temperature for 12 hours after the reaction is finished, washing the obtained product with the deionized water until the pH value is 7, and drying the product to obtain the LDHs/foam nickel precursor Ni with the multilevel layered structure3Fe0.5Al0.5-LDHs/NF; as shown in FIG. 3, the morphology of the layered nanosheets growing on the surface of the foamed nickel can be clearly seen in an SEM (scanning electron microscope) image of the precursor, the bottom layer is a vertically staggered LDHs nanosheet array, the diameter of the LDHs nanosheet array is 60-80 nm, the top layer is a spherical morphology formed by self-assembly of the nanosheets, and the diameter of the nanosheets is 100-150 nm.
And step 3: the precursor obtained in the step (2) is put in H2/Ar(10％H2) Roasting in reducing atmosphere at 500 deg.C with a heating rate of 2 deg.C/min, maintaining at 500 deg.C for 3h, and cooling to room temperature to obtain multi-stage layered Fe-Ni alloy catalyst Ni3Fe0.5Al0.5and/NF. As shown in figure 4, after roasting, the morphology of the nanosheet array which is vertically staggered at the bottom layer is continuously maintained, the size is slightly reduced, the diameter is 50-70 nm, the spherical morphology formed by self-assembly of the nanosheets at the top layer is also continuously maintained, and as shown in figure 5, the diameter of the nanosheets is 80-100 nm, and a plurality of nanoparticles with high dispersion and small particle size can be obviously seen.
And (4) connecting two ends of the multistage layered iron-nickel alloy catalyst obtained in the step (3) into a circuit through a lead by using a constant-current direct-current power supply, loading appropriate current to generate Joule heat, controlling the reaction temperature to be 300 ℃, and driving catalytic reaction.
Example 2:
step 1: cutting the porous foam nickel into pieces with the length of 100mm, the width of 4mm and the thickness of 1mm, and placing the pieces in 6mol/L hydrochloric acid for ultrasonic treatment for 0.3h, wherein the ultrasonic power is 300W. Then continuing to perform ultrasonic treatment in deionized water and absolute ethyl alcohol for 0.3h respectively, and drying in a vacuum drying oven for 6h to obtain a foamed nickel substrate without an oxide layer on the surface;
step 2: 0.012mol of Ni (NO)3)2·6H2O、0.001mol Fe(NO3)3·9H2O、0.003mol Al(NO3)3·9H2Dissolving O, 0.064mol of urea and 0.008mol of citric acid in deionized water at the same time, transferring the solution into a 100ml polytetrafluoroethylene lined kettle, putting the 1 piece of the foamed nickel substrate in the step (1) into the reaction kettle, sealing a kettle cover, putting the kettle cover into a stainless steel kettle skin, screwing the kettle cover, putting the kettle cover into a 140 ℃ blast drying box for hydrothermal reaction, standing the reaction product for 12 hours at room temperature after 8 hours of reaction, washing the obtained product with the deionized water until the pH value is 7, and drying the product to obtain a multistage layered LDHs/foamed nickel precursor Ni precursor with a layered structure3Fe0.25Al0.75-LDHs/NF；
And step 3: putting the precursor in the step (2) in H2/Ar(10％H2) Roasting in reducing atmosphere at 550 deg.C with a heating rate of 1.5 deg.C/min, maintaining at 550 deg.C for 3h, and cooling to room temperature to obtain multi-stage layered Fe-Ni alloy catalyst Ni3Fe0.25Al0.75and/NF, as shown in FIG. 6.
And (4) connecting the whole multi-stage layered iron-nickel alloy catalyst obtained in the step (3) into a circuit through a lead by using a constant-current direct-current power supply, loading proper current to generate Joule heat, controlling the reaction temperature to be 350 ℃, and driving the catalytic reaction.
Example 3:
step 1: cutting the porous foam nickel into pieces with the length of 70mm, the width of 6mm and the thickness of 1mm, and placing the pieces in 3mol/L hydrochloric acid for ultrasonic treatment for 0.5h, wherein the ultrasonic power is 300W. Then continuing to perform ultrasonic treatment in deionized water and absolute ethyl alcohol for 0.25h respectively, and drying in a vacuum drying oven for 6h to obtain a foamed nickel substrate without an oxide layer on the surface;
and 2, step: 0.009mol of Ni (NO)3)2·6H2O、0.001mol Fe(NO3)3·9H2O、0.002mol Al(NO3)3·9H2Dissolving O, 0.048mol of urea and 0.0096mol of citric acid in deionized water simultaneously, transferring the solution into a 100ml polytetrafluoroethylene lining kettle, putting the foamed nickel substrate 1 sheet in the step (1) into the reaction kettle, sealing the kettle cover, putting the kettle cover into a stainless steel kettle skin, screwing the kettle cover, and putting the kettle cover into the stainless steel kettle skin to be screwed, wherein 1 mol of the stainless steel kettle skin is put into the kettle coverCarrying out hydrothermal reaction in a 20 ℃ blast drying oven, standing for 12h at room temperature after 12h of reaction is finished, washing the obtained product with deionized water until the pH value is 7, and drying to obtain the LDHs/foamed nickel precursor Ni with the multi-stage layered structure3Fe0.33Al0.66-LDHs/NF；
And step 3: putting the precursor in the step (2) in H2/Ar(10％H2) Roasting in reducing atmosphere at 600 deg.C with a heating rate of 1 deg.C/min, maintaining at 600 deg.C for 3h, and cooling to room temperature to obtain multi-stage layered Fe-Ni alloy catalyst Ni3Fe0.33Al0.66and/NF, as shown in FIG. 7. The STEM element distribution line scan shown in fig. 8 clearly shows the position distribution of each metal element in the particles, and obviously, all Fe and Ni are distributed at the same position, forming a uniform alloy structure.
And (4) connecting the whole multi-stage layered iron-nickel alloy catalyst obtained in the step (3) into a circuit through a lead by using a constant-current direct-current power supply, loading proper current to generate Joule heat, controlling the reaction temperature to be 400 ℃, and driving the catalytic reaction. As shown in FIG. 9, catalyst Ni3Fe0.33Al0.66/NF vs. Ni alone3Al1/NF higher catalytic CO2Preparation of CH4Active and the catalyst is on CH during the reaction4Is selected at>95％。
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of a multi-stage layered structure iron-nickel alloy catalyst is characterized by comprising the following steps: the preparation method of the iron-nickel alloy catalyst with the multi-stage layered structure comprises the following steps:
(1) taking a high-porosity foamed nickel metal substrate as a conductive support framework, respectively placing the conductive support framework in a hydrochloric acid solution, deionized water and absolute ethyl alcohol for ultrasonic treatment, and drying in a vacuum drying oven for 6 hours to obtain a foamed nickel substrate without an oxide layer on the surface;
(2) dissolving metal salt, urea and citric acid in deionized water at the same time, transferring the solution into a 100ml polytetrafluoroethylene lining, putting the foamed nickel metal substrate obtained in the step (1), sealing the foamed nickel metal substrate, putting the sealed foamed nickel metal substrate into a stainless steel kettle, screwing the sealed foamed nickel metal substrate into a forced air drying oven, carrying out hydrothermal reaction, standing the sealed foamed nickel metal substrate at room temperature after the reaction is finished, washing the obtained product with the deionized water until the pH value of the product is 7, and drying the product to obtain a LDHs/foamed nickel precursor with a multi-stage layered structure;
(3) subjecting the precursor obtained in the step (2) to reaction in H2Roasting in a reducing atmosphere to obtain a corresponding multistage layered iron-nickel alloy catalyst;
the high-porosity foamed nickel metal substrate in the step (1) is 50-100 mm long, 4-6 mm wide, 1-1.5 mm thick and long: the width is not less than 10:1, the porosity is higher than 95%, the concentration of hydrochloric acid is 3-6 mol/L, the ultrasonic power is 300W, and the ultrasonic time is 0.25-0.5 h;
in the step (2), the metal salt includes divalent Ni2+And trivalent Fe3+Trivalent Al3+A metal salt in the form of nitrate or chloride or their mixture, Ni2+And Fe3+、Al3+Has a molar ratio of [ Ni ]2+]/[Fe3++Al3 +]3: 1, the metal salt and urea are in large excess relative to the nickel metal base foam, every 1mmol of divalent Ni2+Corresponds to 10mg of foamed nickel metal substrate; the hydrothermal temperature is selected to be 110-140 ℃, the time is 8-12 h, the room-temperature standing time is 12h, and the drying condition is the same as that of the step (1), so that the hierarchical LDHs/foam nickel precursor Ni with the multilevel structure is obtained3FexAly-LDHs/NF; [ Urea ]]/[Ni2++Fe3++Al3+]=3.33～4；
In the step (3), the roasting conditions are as follows: introduction of H2Roasting the/Ar mixed gas at 500-600 ℃, heating up at a rate of 1-2 ℃/min for 3h to obtain the multi-stage layered Fe-Ni alloy catalyst Ni3FexAly/NF。
2. The method of preparing a multi-stage layered structure iron-nickel alloy catalyst according to claim 1, wherein: the steps are(2) In (Ni)2+And Fe3+、Al3+In the molar ratio of [ Fe ]3+]/[Al3+]=0.33～1。
3. The method of preparing a multi-stage layered structure iron-nickel alloy catalyst according to claim 1, wherein: in the step (2), [ urea ]/[ citric acid ] =5 to 10.
4. The method of preparing a multi-stage layered structure iron-nickel alloy catalyst according to claim 1, wherein: the LDHs/foam nickel precursor with the multi-stage layered structure is expressed as NiFeAl-LDHs/NF, and is characterized in that LDHs nanosheets are ordered and layered and grow on a foam nickel substrate, wherein the LDHs nanosheets at the bottom layer are mutually staggered to form a nanosheet array, the diameter of the nanosheet is 50-100 nm, and the thickness of the nanosheet is 5-10 nm; the top-layer LDHs nanosheets are mutually self-assembled into a spherical shape, the diameter of the nanosheets is 100-300 nm, the thickness of the nanosheets is 8-12 nm, and the nanosheets are in close contact with the bottom-layer nanosheet array, so that the precursor presents a special layered three-dimensional multilevel structure shape; and roasting the precursor, wherein the obtained alloy catalyst still maintains the morphological characteristics, the catalyst is expressed as NiFeAl/NF, all Fe and Ni form small-size alloy particles, and the size of the alloy particles is 5-10 nm.
5. The method for preparing a multi-stage layered structure iron-nickel alloy catalyst according to claim 1, wherein: connecting two ends of the multistage layered iron-nickel alloy catalyst prepared in the step (3) into a circuit through a pure copper wire, loading current to generate joule heat, and driving a catalytic reaction; the current loading range is between 0A and 6A and is not 0A; the voltage loading range is between 0V and 30V and is not 0V; the heat generating temperature of the catalyst is between 150 and 400 ℃.
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| CN111498952B (en) * | 2020-04-09 | 2021-08-17 | 上海交通大学 | Porous carbon iron-nickel alloy foam nickel electrode and preparation method and application thereof |
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| CN112779550B (en) * | 2021-01-11 | 2022-05-17 | 中山大学 | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof |
| CN113023842A (en) * | 2021-03-19 | 2021-06-25 | 西安建筑科技大学 | Method for treating antibiotic wastewater by electrochemically strengthening and catalyzing persulfate |
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