CN107335433B - Preparation method of molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst - Google Patents
Preparation method of molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst Download PDFInfo
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- CN107335433B CN107335433B CN201710672453.2A CN201710672453A CN107335433B CN 107335433 B CN107335433 B CN 107335433B CN 201710672453 A CN201710672453 A CN 201710672453A CN 107335433 B CN107335433 B CN 107335433B
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- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 45
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910015675 MoO3−x Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/399—
-
- 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
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
Abstract
The invention belongs to the technical field of preparation of electrocatalytic hydrogen evolution catalysts, and discloses a preparation method of a molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst. Preparing substoichiometric molybdenum oxide; under a light-tight environment, magnetically stirring molybdenum oxide and a chloroplatinic acid solution for reaction for 1-5 hours, then adding carbon black into the reaction solution, ultrasonically dispersing uniformly, and drying to obtain a molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst; wherein the content of platinum in the chloroplatinic acid solution accounts for 1-10% of the mass of molybdenum oxide, and the mass ratio of the molybdenum oxide to the later-added carbon black is 1: 9-9: 1. The invention breaks through the traditional platinum loading method, realizes platinum deposition in a dark environment, ensures high utilization rate of platinum atoms by compounding with carbon black, has rich raw materials and environment-friendly and pollution-free preparation technology.
Description
Technical Field
The invention belongs to the technical field of preparation of electrocatalytic hydrogen evolution catalysts, and particularly relates to a preparation method of a molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst.
Background
The hydrogen is a clean new energy, the by-product of the hydrogen is water after the hydrogen is used, and the hydrogen has no pollution to the environment, and is one of ideal new energy sources for replacing fossil fuels at present. The main hydrogen production methods include electro-catalytic hydrogen production and photocatalytic hydrogen production, and the electro-catalytic hydrogen production efficiency is high in practical application and easy to implement. However, the efficiency of electrocatalytic hydrogen evolution depends on the selection of electrocatalysts, and at present, the commercialized high-efficiency catalyst is mainly a platinum-carbon catalyst, but the utilization efficiency of platinum is low. When preparing the high-efficiency platinum-supported electrocatalyst, the traditional preparation methods such as a reducing agent reduction deposition method and a light deposition method are adopted. In the preparation and application of the platinum-supported electrocatalyst, it is still a challenge to utilize simple and easily available raw materials and to explore a simpler preparation technology in order to reduce the production cost and achieve the purpose of green environmental protection.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum oxide-based high-efficiency electrocatalytic hydrogen evolution catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a molybdenum oxide-based high-efficiency electrocatalytic hydrogen evolution catalyst comprises the following steps:
(1) preparing substoichiometric molybdenum oxide; by substoichiometric molybdenum oxide is meant molybdenum oxide that is not stoichiometric MoO3Containing not only molybdenum in the +6 state but also molybdenum in a lower valence state, i.e. of a formula other than MoO3Instead, is MoO3-x；
(2) Magnetically stirring and reacting the molybdenum oxide obtained in the step (1) with a chloroplatinic acid solution for 1-5 hours in a light-tight environment, then adding carbon black into the reaction solution, ultrasonically dispersing uniformly, and drying to obtain a molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst; wherein the content of platinum in the chloroplatinic acid solution accounts for 1-10% of the mass of molybdenum oxide, and the mass ratio of the molybdenum oxide to the later-added carbon black is 1: 9-9: 1.
Preferably, the concentration of the chloroplatinic acid solution is 46.6 mmol/L.
Preferably, the content of platinum in the chloroplatinic acid solution accounts for 6 percent of the mass of the molybdenum oxide, and the mass ratio of the molybdenum oxide to the carbon black added at the later stage is 1: 1.
Step (1) of the present invention can be prepared according to the prior art, such as but not limited to the method for preparing amorphous molybdenum oxide nanosheets disclosed in the invention patent (application No. 201611140260.4) filed on 2016, 12 and 12, wherein the amorphous molybdenum oxide nanosheets obtained by the preparation method are substoichiometric molybdenum oxide.
The invention provides a preparation method of a molybdenum oxide-based high-efficiency electrocatalytic hydrogen evolution catalyst. The substoichiometric molybdenum oxide is rich in oxygen defects, is easy to generate oxidation reaction, has certain reducibility, and can reduce the subsequently added chloroplatinic acid solution, so that the high-dispersion platinum nanocrystals are loaded on the molybdenum oxide substrate, and high catalytic activity is ensured. The introduction of the high-conductivity carbon black material further improves the conductivity of the material, improves the utilization rate of the catalyst, and ensures the high efficiency of the catalyst on the premise of low platinum loading capacity. From the whole preparation process, the invention breaks through the traditional platinum loading method, realizes platinum deposition in a dark environment, ensures high utilization rate of platinum atoms by compounding with carbon black, has rich raw materials and environment-friendly and pollution-free preparation technology, and has great application prospect in the field of energy conversion.
Drawings
FIG. 1 is an XPS characterization picture of Mo of sub-stoichiometric molybdenum oxide prepared in example 1 of the present invention.
Fig. 2 is an HRTEM picture of a platinum nanocrystal supported molybdenum oxide nanosheet synthesized in example 1 of the present invention.
Fig. 3 is an LSV diagram of the electro-catalytic hydrogen evolution of the molybdenum oxide-based highly efficient electro-catalytic hydrogen evolution catalyst prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a molybdenum oxide-based high-efficiency electrocatalytic hydrogen evolution catalyst comprises the following steps:
(1) the method for preparing the substoichiometric molybdenum oxide according to the embodiment 1 in CN201611140260.4 comprises the following specific steps:
filling 10ml of 45% (volume ratio, the same below) ethanol into a beaker, dispersing 100mg of molybdenum sulfide into 10ml of 45% ethanol, then carrying out ultrasonic treatment on the beaker containing the solution in water bath for 4 hours, drying the beaker in a drying oven, and calcining the beaker in a carbonization furnace at 350 ℃ for 90min in an air environment, wherein the heating rate is 10 ℃ per minute; dispersing the calcined product in 45% ethanol, ultrasonically dispersing for 1h again, transferring to a reaction kettle, injecting carbon dioxide into the reaction kettle to reach a supercritical state (16 Mpa, 80 ℃), and reacting for 3h under magnetic stirring; transferring the sample subjected to supercritical treatment to a 50ml centrifuge tube, centrifuging at 6000 rpm by using a centrifuge for 5min to obtain supernatant, and drying to obtain substoichiometric molybdenum oxide, wherein an XPS (XPS) representation diagram of Mo of the substoichiometric molybdenum oxide is shown in FIG. 1; from XPS spectra it is not expected that the samples are stoichiometricOf MoO3The substoichiometric nature of the molybdenum oxide produced is confirmed by the fact that the sample contains not only molybdenum in the valence state 6 (corresponding to two binding energies: 235.6 eV and 232.4 eV), but also certain molybdenum in the valence state 5 (corresponding to two binding energies: 234.4 eV and 231.2 eV);
(2) mixing 10 mg of molybdenum oxide obtained in the step (1) with 66 mu L of 46.6 mmol/L chloroplatinic acid solution at room temperature in a dark environment, magnetically stirring for reaction for 3 hours, sampling at the moment, characterizing by a transmission electron microscope, then adding commercial carbon black into the rest reaction solution, ultrasonically dispersing for 30min, sampling at the moment, characterizing by electrocatalytic hydrogen evolution, and drying the rest part to obtain the molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst; wherein, the content of platinum in the chloroplatinic acid solution accounts for 6 percent of the mass of molybdenum oxide, and the mass ratio of the molybdenum oxide to the carbon black added in the later period is 1: 1.
The samples were characterized on the carbon support film by transmission electron microscopy, with HRTEM in figure 2, clearly seen in the high resolution transmission: nanometer crystal grains of platinum are uniformly dispersed on a substrate of the molybdenum oxide nanometer sheet, and the size of the nanometer crystal grains is about 2nm, which shows that chloroplatinic acid is successfully reduced to generate simple substance platinum under the condition of keeping out of the sun.
The sample is characterized by electrocatalytic hydrogen evolution by using an electrochemical workstation (CHI 660E), the electrolyte is 0.5mol/L sulfuric acid, a carbon rod is used as a counter electrode, Ag/AgCl is used as a reference electrode, a working electrode is a glassy carbon electrode, and the loading amount of a catalyst on the working electrode is 0.1 mg/cm2(meanwhile, a commercial 20% Pt/C catalyst is used as a control catalyst, the mass percentage of Pt in the control catalyst is 20%, and when the 20% Pt/C catalyst is loaded, absolute ethyl alcohol is used as a dispersing agent), a hydrogen evolution test is carried out by using a Linear Sweep Voltammetry (LSV), and the LSV is shown in figure 3, and can be known as follows: the catalyst prepared by the invention achieves the current density of-10 mA/cm2The overpotential at this time was the same as that of the commercial but the initial potential was lower than 20% Pt/C, indicating that the inventive samples exhibited excellent electrocatalytic hydrogen evolution performance while having a low platinum content.
Claims (1)
1. A preparation method of a molybdenum oxide-based high-efficiency electrocatalytic hydrogen evolution catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing substoichiometric molybdenum oxide;
(2) magnetically stirring the molybdenum oxide obtained in the step (1) and a chloroplatinic acid solution for reaction for 3 hours in a light-tight environment, then adding carbon black into the reaction solution, ultrasonically dispersing uniformly, and drying to obtain a molybdenum oxide-based efficient electrocatalytic hydrogen evolution catalyst; wherein the concentration of the chloroplatinic acid solution is 46.6 mmol/L, the content of platinum in the chloroplatinic acid solution accounts for 6 percent of the mass of molybdenum oxide, and the mass ratio of the molybdenum oxide to the later-added carbon black is 1: 1.
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| CN110773162A (en) * | 2019-11-04 | 2020-02-11 | 青岛大学 | Preparation method and application of carbon-coated two-dimensional layered molybdenum oxide compound-supported noble metal |
| CN110967331B (en) * | 2019-12-06 | 2022-06-10 | 华东理工大学 | Oxidation-reduction-resistant amorphous MoO for SERS substrate3-xPreparation method and application of nanosheet |
| CN110961101B (en) * | 2019-12-24 | 2022-12-06 | 西南大学 | Platinum-based catalyst, preparation method and application thereof |
| CN113198455B (en) * | 2021-05-17 | 2022-12-09 | 南昌航空大学 | Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof |
| CN113750987A (en) * | 2021-09-16 | 2021-12-07 | 南京信息工程大学 | Quadrature phase MoO3Electrocatalyst and preparation method and application thereof |
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| CN101814608A (en) * | 2010-04-29 | 2010-08-25 | 华南师范大学 | Anode composite catalyst Pt-MoOx for direct methanol fuel cells, and preparation method thereof |
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