CN110586085A - Method for preparing metal mesh catalyst - Google Patents
Method for preparing metal mesh catalyst Download PDFInfo
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- CN110586085A CN110586085A CN201910981317.0A CN201910981317A CN110586085A CN 110586085 A CN110586085 A CN 110586085A CN 201910981317 A CN201910981317 A CN 201910981317A CN 110586085 A CN110586085 A CN 110586085A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 180
- 239000004005 microsphere Substances 0.000 claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 89
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 79
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 229910018949 PtAu Inorganic materials 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910002836 PtFe Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Abstract
The invention discloses a method for preparing a metal mesh catalyst, which comprises the following steps: step S110, preparing a silicon dioxide microsphere template; step S120, preparing a regularly arranged silicon dioxide microsphere matrix; step S130, reducing metal; and step S140, removing the template by acid washing. Has the advantages that: the preparation method comprises the steps of preparing silicon dioxide microspheres, using the regularly-displayed silicon dioxide microspheres as a template, reducing metal in the ordered silicon sphere template by adopting a dipping reduction method, and removing the silicon dioxide microsphere template by acid washing to obtain a metal mesh catalyst, so that the specific surface area of the catalyst is increased; the prepared metal mesh catalyst has adjustable mesh size, can also improve the solute transmission process in the catalysis process, accelerates the contact of the catalyst and reactants, ensures that the catalytic reaction is carried out more fully, and has better catalytic activity compared with the existing catalyst.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a method for preparing a metal mesh catalyst.
Background
Excessive consumption of energy also presents a series of challenges, as traditional fossil resources are unable to meet the rapidly growing energy demand. In order to solve energy and environmental problems, the development of renewable and sustainable energy storage/conversion technologies is urgently required. The electrochemical energy conversion device can obviously reduce the dependence on fossil fuels and optimize the prior energy structure. Compared with the traditional fossil fuel, the electrochemical energy conversion and storage devices such as fuel cells, hydrolysis devices, metal air batteries, CO2/N2 fixing technologies and the like have higher efficiency and clean performance, and have important prospects for solving the current energy and environmental problems. Among them, the key problem that restricts the development of these new energy technologies is the development of efficient, low-cost electrocatalysts.
Electrochemical reactions involving gases occur at the three phase boundary regions of solid electrocatalysts, liquid electrolytes, gaseous reactants and intermediates, where electrons, ions and molecules can be transferred at catalytically active sites. In the prior art, the development of a new generation of electrocatalysts has mainly focused on manipulating the composition, size, porosity and interfacial structure of the material to promote multi-proton coupled electron transfer and mass transfer in electrocatalysis. Altering the electronic properties and structure of the catalyst can affect the adsorption behavior of the reactants and can modulate the catalytic activity. The specific activity of the catalyst can be accelerated by using a high efficiency catalyst to adjust the intrinsic adsorption energy of these reaction intermediates, and the surface properties of the electrocatalyst determine the efficiency of the electrocatalytic reaction. The specific surface area of the catalyst is one of the important indicators of the performance of the catalyst. The extremely large surface area can increase the contact area of the catalyst and reactants, so that the catalytic reaction is carried out more fully, and the catalytic performance is improved. Based on the catalyst structure, the specific surface area can be improved.
Disclosure of Invention
The present invention is directed to a method for preparing a metal mesh catalyst to solve the above problems, and a preferred embodiment of the present invention includes: by adopting a template method, the arranged silicon dioxide microspheres are used as templates, and the metal precursor solution is dipped, so that the metal grid catalyst is synthesized, the specific surface area of the catalyst is improved, and the like, and the technical effects are described in detail below.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, preparing a silicon dioxide microsphere template, preparing a mixed solution of ethanol, water and ammonia water, uniformly mixing, adding tetraethoxysilane, fully reacting, stirring, centrifuging, cleaning, heating and drying to obtain silicon dioxide microspheres, namely the silicon dioxide microsphere template for preparing the metal mesh catalyst;
step S120, preparing a regularly arranged silicon dioxide microsphere matrix, putting the silicon dioxide microspheres prepared in the step a into a beaker, adding ethanol, stirring until the silicon dioxide microspheres are uniformly dispersed to form a solution, putting the flaky carrier into the solution, and drying the solution to obtain the regularly arranged silicon dioxide microsphere matrix on the surface of the carrier;
step S130, metal reduction, namely reducing metal in the silicon dioxide microsphere matrix prepared in the step b by adopting a dipping reduction method to obtain a metal mesh catalyst matrix;
and S140, removing the template by acid washing, wherein the metal mesh catalyst substrate obtained in the step S130 is acid washed, and the silicon dioxide microsphere template is removed to obtain the metal mesh catalyst.
Preferably, in the step S110, the volume mixing ratio of the ethanol, the water and the ammonia water in the mixed solution is 50-150:5-20: 2-8;
the volume fraction of the ethyl orthosilicate is 4-40.
Preferably, the size of the silica microspheres prepared in step S110 is 50nm to 500 nm.
Preferably, the drying latitude in the step S110 is 30 ℃ to 80 ℃.
Preferably, the step S130 includes the following operations:
operation S131, dissolving metal salt to obtain a metal salt solution, placing the silicon dioxide microsphere matrix obtained in the step S120 into the metal salt solution to react, and obtaining a sediment;
operation S132, taking out the sediment communicated silica microsphere matrix, and putting the sediment communicated silica microsphere matrix into an oven for drying to obtain a dried sample;
and operation S133, placing the sample into a tube furnace for heating, and introducing hydrogen to reduce the metal in the sample to obtain the metal grid catalyst substrate.
Preferably, in operation S133, the heating temperature of the tube furnace is 160 to 800 ℃, and the heating time is 1 to 10 hours.
Preferably, the metal salt is one or more of Pt, Au, Co, Fe, Ni, Ru, and Ag salts.
Preferably, in step S140, the acid for pickling is hydrofluoric acid, the concentration of the hydrofluoric acid is 10 to 50wt%, and the pickling time is 4 to 50 hours.
In conclusion, the beneficial effects of the invention are as follows: 1. the preparation method comprises the steps of preparing silicon dioxide microspheres, using the regularly-displayed silicon dioxide microspheres as a template, reducing metal in the ordered silicon sphere template by adopting a dipping reduction method, and removing the silicon dioxide microsphere template by acid washing to obtain a metal mesh catalyst, so that the specific surface area of the catalyst is increased;
2. the prepared metal mesh catalyst has adjustable mesh size, can also improve the solute transmission process in the catalysis process, accelerates the contact of the catalyst and reactants, ensures that the catalytic reaction is carried out more fully, and has better catalytic activity compared with the existing catalyst.
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 present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern (XRD) of Pt, PtPd and PtAu catalysts, (FIG. 1 includes three figures a, b, c);
FIG. 2 is a Scanning Electron Microscope (SEM) surface topography of Pt, PtPd and PtAu catalysts of different mesh sizes (FIG. 2 includes three graphs a, b, c);
FIG. 3 is a graph showing the catalytic activity of PtPd catalysts for oxygen reduction reactions under acidic conditions;
fig. 4 shows the catalytic activity of the PtAu catalyst for glucose oxidation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The specific embodiment is as follows:
example 1:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 50ml of absolute ethyl alcohol, 10ml of water and 2ml of ammonia water into a beaker, uniformly mixing the solution, putting the mixed solution into a constant-temperature heating magnetic stirrer, quickly adding 30ml of tetraethoxysilane into the beaker after stirring for 1 hour, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 30 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 5g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 50ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
s130, diluting chloroplatinic acid into a solution of 5mol/L by using absolute ethyl alcohol, dropwise adding 5ml of the solution into a beaker containing a silica microsphere template, naturally settling for a period of time, and then drying in a vacuum oven at 60 ℃; after the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 300 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 8 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 8 hours by using a hydrofluoric acid solution with the mass concentration of 15% to remove the template, and obtaining the metal Pt mesh catalyst. In the a diagram of fig. 1, the (111), (200), (220) and (311) crystal planes of Pt corresponding to 39.76 °, 46.24 °, 67.45 ° and 81.24 ° can be seen, illustrating that Pt metal can be obtained by the process of the present invention.
And (3) observing the surface appearance: the surface morphology of the Pt catalyst was observed by using a scanning electron microscope, and as a result, as shown in a diagram of fig. 2, it can be seen that by the preparation method, a Pt regular grid structure can be synthesized.
Example 2:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 100ml of absolute ethyl alcohol, 5ml of water and 4ml of ammonia water into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 5ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 50 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 20ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
s130, preparing chloroplatinic acid into a precursor solution of 5m mol/L, and preparing palladium chloride into a precursor solution of 5m mol/L. Respectively putting 2.5ml of chloroplatinic acid and palladium chloride solution into a beaker, putting the beaker into an ultrasonic machine for ultrasonic mixing for 30 minutes, dropwise adding 5ml of solution into the beaker containing a silica microsphere template, naturally settling for a period of time, and then putting the beaker into a vacuum oven at 30 ℃ for drying. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 600 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 40 hours by using a hydrofluoric acid solution with the mass concentration of 50% to remove the template, so as to obtain the metal PtPd mesh catalyst. In the b diagram of fig. 1, the (111), (200), (220) and (311) crystal planes of Pt and Pd at 39.76 °, 46.24 °, 67.45 ° and 81.24 ° can be seen, indicating that PtPd metal can be obtained by the process of the present invention.
And (3) observing the surface appearance: the surface morphology of the PtPd catalyst was observed by SEM, and the result is shown in b in fig. 2. It can be seen in the b diagram in fig. 2 that by this preparation method, a Pt-structured lattice structure can be synthesized.
And (3) investigating catalytic performance: an LSV test was performed in 0.1M perchloric acid at 1600 rpm, and the results are shown in FIG. 3, where it was found that the PtPd alloy catalyst has a good catalytic activity for the oxygen reduction reaction.
Example 3:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, taking 150ml of absolute ethyl alcohol, 20ml of water and 8ml of ammonia water, putting the solution into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 20ml of tetraethoxysilane into the beaker after stirring for 1 hour, continuously stirring for 5 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 60 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 15g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 150ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in a solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
s130, diluting chloroauric acid into a solution of 5m mol/L by using absolute ethyl alcohol, dropwise adding 5ml of the solution into a beaker containing a silica microsphere template, naturally settling for a period of time, and then drying in a vacuum oven at 80 ℃; after the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 800 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 20 hours by using a hydrofluoric acid solution with the mass concentration of 50% to remove the template, and obtaining the metal Au grid catalyst.
Example 4:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 100ml of absolute ethyl alcohol, 20ml of water and 5ml of ammonia water into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 10ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 80 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 10ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
s130, preparing chloroplatinic acid into a precursor solution of 5m mol/L, and preparing chloroauric acid into a precursor solution of 5m mol/L. Respectively putting 3ml of chloroplatinic acid and palladium chloride solution into a beaker, putting the beaker into an ultrasonic machine, ultrasonically mixing for 30 minutes, dropwise adding 6ml of solution into the beaker containing a silica microsphere template, naturally settling for a period of time, and then putting the beaker into a vacuum oven at 30 ℃ for drying. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 800 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 5 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature by using a hydrofluoric acid solution with the mass concentration of 20% for 10 hours to remove the template, thereby obtaining the metal PtAu grid catalyst. Structural analysis: the structure of the metal PtAu grid was analyzed by XRD. The (111), (200) and (220) crystallographic planes of Pt and Au, respectively, can be seen in the c diagram of FIG. 1, illustrating that PtAu metal can be obtained by the method of the present invention.
And (3) observing the surface appearance: the surface morphology of the PtAu catalyst was observed by SEM, and the result is shown in fig. 2 c, in which it can be seen that by this preparation method, a PtAu regular lattice structure can be synthesized.
And (3) investigating catalytic performance: the sweep rate was 50mV/s, and the cyclic voltammogram measured in PBS buffer containing 10mM glucose is shown in FIG. 4, and it was found that the PtAu alloy catalyst had better catalytic activity for the glucose oxidation reaction.
Example 5:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 100ml of absolute ethyl alcohol, 20ml of water and 5ml of ammonia water into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 10ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 80 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 10ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
and S130, preparing the silver chloride into a precursor solution of 5m mol/L. 5ml of the solution is dripped into a beaker containing a silicon dioxide microsphere template, naturally settled for a period of time and then dried in a vacuum oven at 30 ℃. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 600 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 8 hours by using a hydrofluoric acid solution with the mass concentration of 50% to remove the template, and obtaining the metal Ag mesh catalyst.
Example 6:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 100ml of absolute ethyl alcohol, 10ml of water and 4ml of ammonia water into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 30ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 70 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 10ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
and S130, preparing the cobalt chloride into a precursor solution of 5m mol/L, and preparing the nickel chloride into a precursor solution of 5m mol/L. Respectively putting 2ml of chloroplatinic acid and palladium chloride solution into a beaker, putting the beaker into an ultrasonic machine, ultrasonically mixing for 30 minutes, dropwise adding 4ml of solution into the beaker containing a silica microsphere template, naturally settling for a period of time, and then putting the beaker into a vacuum oven at 70 ℃ for drying. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 800 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 10 hours by using a hydrofluoric acid solution with the mass concentration of 10% to remove the template, thereby obtaining the metal CoNi grid catalyst.
Example 7:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, putting 50ml of absolute ethyl alcohol, 10ml of water and 8ml of ammonia water into a beaker, uniformly mixing the solution, putting the mixed solution into a constant-temperature heating magnetic stirrer, quickly adding 10ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 60 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 10ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
step S130, preparing ruthenium chloride into a precursor solution of 5m mol/L. 5ml of the solution is dripped into a beaker containing a silicon dioxide microsphere template, naturally settled for a period of time and then dried in a vacuum oven at 80 ℃. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 800 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature for 8 hours by using a hydrofluoric acid solution with the mass concentration of 30% to remove the template, and obtaining the metal Ru grid catalyst.
Example 8:
the invention provides a method for preparing a metal mesh catalyst, which comprises the following steps:
step S110, taking 150ml of absolute ethyl alcohol, 20ml of water and 2ml of ammonia water, putting the solution into a beaker, uniformly mixing the solution, putting the solution into a constant-temperature heating magnetic stirrer, quickly adding 20ml of tetraethoxysilane into the beaker after stirring for 2 hours, continuously stirring for 3 hours, centrifugally cleaning the sample after stirring, and finally putting the sample into a vacuum oven at 50 ℃ for drying to obtain silicon dioxide microspheres;
step S120, taking 2g of silicon dioxide microspheres, putting the silicon dioxide microspheres into a beaker, adding 10ml of ethanol, stirring to uniformly disperse the silicon dioxide microspheres in the solution, putting a glass sheet serving as a carrier into the solution, and drying to regularly arrange the silicon dioxide microspheres on the surface of the glass sheet to obtain regularly arranged silicon dioxide microspheres;
s130, preparing chloroplatinic acid into a precursor solution of 5m mol/L, and preparing ferric chloride into a precursor solution of 5m mol/L. Respectively putting 2ml of chloroplatinic acid and palladium chloride solution into a beaker, putting the beaker into an ultrasonic machine, ultrasonically mixing for 30 minutes, dropwise adding 4ml of solution into the beaker containing a silica microsphere template, naturally settling for a period of time, and then putting the beaker into a vacuum oven at 50 ℃ for drying. After the sample is dried, putting the sample into a vacuum tube furnace, firstly introducing argon until the temperature is raised to 800 ℃, then closing the argon and introducing hydrogen, and preserving the heat for 10 hours;
and step S140, magnetically stirring the product obtained in the step S130 at room temperature by using a hydrofluoric acid solution with the mass concentration of 40% for 10 hours to remove the template, thereby obtaining the metal PtFe mesh catalyst.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A method of making a metal mesh catalyst comprising the steps of:
step S110, preparing a silicon dioxide microsphere template, preparing a mixed solution of ethanol, water and ammonia water, uniformly mixing, adding tetraethoxysilane, fully reacting, stirring, centrifuging, cleaning, heating and drying to obtain silicon dioxide microspheres, namely the silicon dioxide microsphere template for preparing the metal mesh catalyst;
step S120, preparing a regularly arranged silicon dioxide microsphere matrix, putting the silicon dioxide microspheres prepared in the step a into a beaker, adding ethanol, stirring until the silicon dioxide microspheres are uniformly dispersed to form a solution, putting the flaky carrier into the solution, and drying the solution to obtain the regularly arranged silicon dioxide microsphere matrix on the surface of the carrier;
step S130, metal reduction, namely reducing metal in the silicon dioxide microsphere matrix prepared in the step b by adopting a dipping reduction method to obtain a metal mesh catalyst matrix;
and S140, removing the template by acid washing, wherein the metal mesh catalyst substrate obtained in the step S130 is acid washed, and the silicon dioxide microsphere template is removed to obtain the metal mesh catalyst.
2. The method of claim 1, wherein the method comprises: in the step S110, the volume mixing ratio of the ethanol, the water and the ammonia water in the mixed solution is 50-150:5-20: 2-8;
the volume fraction of the ethyl orthosilicate is 4-40.
3. The method of claim 1, wherein the method comprises: the size of the silica microspheres prepared in the step S110 is 50nm-500 nm.
4. The method of claim 1, wherein the method comprises: the drying latitude in the step S110 is 30-80 ℃.
5. The method of claim 1, wherein the method comprises: the step S130 includes the following operations:
operation S131, dissolving metal salt to obtain a metal salt solution, placing the silicon dioxide microsphere matrix obtained in the step S120 into the metal salt solution to react, and obtaining a sediment;
operation S132, taking out the sediment communicated silica microsphere matrix, and putting the sediment communicated silica microsphere matrix into an oven for drying to obtain a dried sample;
and operation S133, placing the sample into a tube furnace for heating, and introducing hydrogen to reduce the metal in the sample to obtain the metal grid catalyst substrate.
6. The method of claim 5, wherein the metal mesh catalyst is prepared by: in operation S133, the heating temperature of the tube furnace is 160 to 800 ℃, and the heating time is 1 to 10 hours.
7. The method of claim 5, wherein the metal mesh catalyst is prepared by: the metal salt is one or more than two of Pt, Au, Co, Fe, Ni, Ru and Ag salt.
8. The method of claim 1, wherein the method comprises: in the step S140, the acid for pickling is hydrofluoric acid, the concentration of the hydrofluoric acid is 10-50wt%, and the pickling time is 4-50 hours.
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