CN110124707B - Spiral ultralow platinum loading Mo2C catalyst and preparation method and application thereof - Google Patents
Spiral ultralow platinum loading Mo2C catalyst and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 84
- 229910003178 Mo2C Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000011068 loading method Methods 0.000 title claims description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000004070 electrodeposition Methods 0.000 claims abstract description 20
- 238000009713 electroplating Methods 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 33
- 239000004744 fabric Substances 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 15
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 13
- 229940010552 ammonium molybdate Drugs 0.000 claims description 13
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 13
- 239000011609 ammonium molybdate Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- 229910001260 Pt alloy Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- -1 transition metal carbides Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 3
- 229910039444 MoC Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019020 PtO2 Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
The invention relates to spiral ultra-low platinum load Mo2C catalyst, preparation method and application thereof. The preparation method comprises the following steps: s1: preparation of spiral MoO by electrodeposition technology2A precursor; s2: preparation of spiral Mo by chemical vapor deposition2C, a catalyst; s3: method for preparing spiral ultralow platinum load Mo by using electroplating method2And C, a catalyst. The spiral ultra-low platinum load Mo prepared by the invention2The spiral shape of the C catalyst avoids the agglomeration and sintering of the catalyst, has high hydrogen evolution activity, and can be directly used as an integrated electrode to participate in the water electrolysis reaction. The preparation method disclosed by the invention is simple and feasible in preparation flow and good in repeatability, greatly reduces the preparation cost of the hydrogen evolution catalyst, and has important practical application value.
Description
Technical Field
The invention belongs to the field of hydrogen production by electrocatalysis electrolysis of water, and particularly relates to spiral Mo with ultralow platinum loading2C catalyst, preparation method and application thereof.
Background
As the global consumption of fossil energy and the resulting climate change problem have become more severe in recent years, the development and utilization of sustainable new energy is receiving increased attention and attention from society. Among them, the hydrogen fuel cell is a new star in the future new energy field due to its advantages of high energy conversion efficiency, large energy density, large power, long power supply time, long service life, no harmful emissions and the like. The anode reactant hydrogen of the fuel cell has the characteristics of high energy density, environmental protection and the like, is one of the key points of the development of new energy fields in the future, and the wide application of hydrogen energy has great strategic significance for solving the energy crisis and the climate problem caused by excessive emission of greenhouse gases.
At present, hydrogen is mainly produced from fossil fuel, and the hydrogen production process can discharge a large amount of greenhouse gas in the production process, thereby causing serious environmental pollution and consuming a large amount of fossil fuel, which is contrary to the aim of utilizing clean energy. In the existing hydrogen production technology, water resources with wide sources are used as raw materials for hydrogen production by water electrolysis, so that the method has the advantages of high efficiency, cleanness and no pollution, and is the most promising hydrogen production approach in the future. The hydrogen production by water electrolysis includes an Oxygen Evolution Reaction (OER) at the anode and a Hydrogen Evolution Reaction (HER) at the cathode. However, the main technical bottleneck of hydrogen production by water electrolysis is that energy consumption is too high, a large amount of electric energy is consumed, and the best HER catalyst at present is a platinum-based catalyst, so that the platinum-based catalyst is difficult to be widely applied in the field of industrial hydrogen production due to scarcity of surface storage of platinum metal and high price. Therefore, research on the use of novel low-cost high-performance catalysts to reduce or even replace platinum-based catalysts becomes a hot spot of current research in the field of hydrogen production by water electrolysis.
In recent years, researchers have made intensive studies on transition metal carbides, sulfides and phosphides as substitutes for platinum-based catalysts, among which transition metal molybdenum (Mo) and compounds thereof are one of the non-noble metal catalysts that have attracted much attention in the HER field. Molybdenum carbide (Mo)2C) Due to the characteristics of similar electronic structure of the d orbitals of the outer layer and the electronic structure of the d orbitals of the platinum group elements and high electron transfer rate, the molybdenum carbide has very excellent hydrogen production performance by electrolyzing water. However, in the current research field, the performance and stability of molybdenum carbide catalysts are still far from those of platinum-based catalysts.
To further promote Mo2Of non-noble metal catalysts such as CThe hydrogen evolution performance is controlled, the production cost of the catalyst is controlled, a trace amount of noble metal platinum is loaded on the catalyst, and the preparation of the ultra-low platinum loading catalyst to replace the traditional platinum-based catalyst becomes the popular research direction in the field of HER catalysts at present.
Disclosure of Invention
The invention aims to overcome the defect and defect of large difference between hydrogen evolution activity of non-noble metal hydrogen evolution catalyst and platinum-based catalyst in the prior art, and provides a spiral ultralow-platinum-loading Mo2And C, a preparation method of the catalyst. According to the invention, the effective catalytic component is spirally wrapped on the carbon cloth fiber, the spiral structure ensures that the catalyst does not have the phenomenon of reducing the catalytic activity due to the fact that clusters are sintered, meanwhile, the spiral surface structure enlarges the contact area of the catalyst and provides a considerable number of active sites, so that the catalyst has excellent hydrogen evolution activity; the preparation method has simple process, and the prepared catalyst and Mo2Compared with the traditional commercialized platinum-carbon catalyst, the catalyst C has greatly improved hydrogen evolution performance, greatly reduced platinum loading capacity and reduced cost, and provides a feasible scheme for reducing the high cost of the hydrogen production by water electrolysis. In addition, the catalyst is an integrated electrode containing effective catalytic components, can be used as a working electrode to participate in water electrolysis reaction, and is suitable for wide application in the field of hydrogen production by water electrolysis.
Another object of the present invention is to provide a spiral ultra-low platinum loading Mo2And C, a catalyst.
Another object of the present invention is to provide the above-mentioned spiral ultra-low platinum Mo load2The application of the C catalyst in the field of electrocatalytic hydrogen evolution.
In order to achieve the purpose, the invention adopts the following technical scheme:
spiral ultralow platinum loading Mo2The preparation method of the catalyst C comprises the following steps:
s1: spiral MoO2Preparing a precursor: depositing on a rod-shaped conductive substrate by adopting an electrodeposition technology to obtain spiral MoO2A precursor;
S2：spiral Mo2C, preparation of a catalyst: subjecting the spiral MoO2Precursor in Ar/H2Keeping the temperature of 700-1000 ℃ for 50-100 min in the mixed gas atmosphere, then introducing hydrocarbon gas, and cooling to obtain spiral Mo2C, a catalyst;
s3: spiral ultra-low platinum loading Mo2C, preparation of a catalyst: in the spiral Mo2Electroplating platinum on the C catalyst, washing and drying to obtain the spiral ultralow platinum-loading Mo2And C, a catalyst.
The invention obtains spiral MoO on a rod-shaped conductive substrate by utilizing an electrodeposition mode2A precursor; then MoO is caused by chemical vapor deposition2Conversion of precursor into Mo2C, then in the form of a spiral Mo2The catalyst with excellent hydrogen evolution performance can be obtained by electroplating and loading ultra-low amount of platinum on the catalyst C, and the whole preparation method has simple process. Due to the spiral structure, the phenomenon that the catalytic activity is reduced due to the fact that the catalyst is not sintered clusters is guaranteed, meanwhile, the effective catalytic components are wrapped on the rod-shaped conductive substrate in a spiral mode, the spiral surface structure enlarges the contact area of the catalyst and provides a considerable number of active sites, and the catalyst has excellent hydrogen evolution activity; the catalyst prepared by the method and Mo2Compared with the traditional commercialized platinum-carbon catalyst, the catalyst C has greatly improved hydrogen evolution performance, greatly reduced platinum loading capacity and reduced cost, and provides a feasible scheme for reducing the high cost of the hydrogen production by water electrolysis.
In addition, the catalyst is an integrated electrode containing effective catalytic components, can be used as a working electrode to participate in water electrolysis reaction, and is suitable for wide application in the field of hydrogen production by water electrolysis.
In general, once platinum is loaded, Mo can be achieved2The improvement of the hydrogen evolution performance of the C catalyst, in the invention, the meaning of the ultralow platinum loading is that the platinum loading is not higher than 15 mu g/cm2。
Preferably, the electrodeposition in S1 is carried out in a constant current cathodic electrodeposition mode, carried out in a two-electrode electrolytic cell.
More preferably, the working electrode of the double-electrode electrolytic cell is a rod-shaped conductive substrate, the counter electrode is a conductive carbon material, and the electrolyte is an ammonium molybdate solution.
Most preferably, the conductive substrate is carbon cloth fiber.
Most preferably, the conductive carbon material is a carbon rod, a carbon cloth, or a carbon paper.
Most preferably, the concentration of the ammonium molybdate solution is 5-15 mmol/L.
More preferably, the impressed constant current of the constant current cathode electrodeposition is 2-8 mA/cm2The electrodeposition time is 10-50 min.
Preferably, S2Ar/H2H in mixed gas atmosphere2The volume fraction of (A) is 2-20%. Inevitably, the volume fraction of Ar is 80-98%.
Preferably, Ar/H in S22The mixed gas atmosphere is obtained by the following process: introduction of Ar/H2After the mixed gas is exhausted, continuously introducing Ar/H2Mixing the gas; introduction of Ar/H2The flow rate of the mixed gas is 100-200 sccm.
Preferably, the flow rate of the hydrocarbon gas introduced into S2 is 20-60 sccm, and the introduction time is 10-120 min; the cooling rate is 2-10 ℃/min.
Preferably, the hydrocarbon gas is one or more of methane, ethane or propane.
More preferably, the hydrocarbon gas is methane; the purity of the methane is 99.9999%.
Preferably, the temperature in S2 is raised to 700-1000 ℃ at a speed of 2-10 ℃/min.
Preferably, platinum is electroplated in S3 using a three-electrode electrolytic cell.
More preferably, the working electrode selected by the three-electrode electrolytic cell is spiral Mo2C catalyst, counter electrode of platinum and electrolyte of H2SO4And (3) solution.
Most preferably, the metallic platinum is a platinum metal sheet, a platinum metal wire or a platinum metal block.
Most preferablyGround, H2SO4The concentration of the solution is 0.2-1.0 mol/L.
Preferably, the platinum electroplating method is a cyclic voltammetry scanning electroplating method, the scanning voltage is 0-0.7V vs. RHE, the scanning speed is 20-100 mV/s, and the electroplating time is 8-14 h.
The electroplating conditions can be adjusted according to actual conditions, so that the loading amount of platinum in the catalyst is proper.
Spiral ultralow platinum loading Mo2C, the catalyst is prepared by the preparation method.
The spiral ultra-low platinum loading Mo2The application of the C catalyst in the field of electrocatalytic hydrogen evolution is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the effective catalytic component in the hydrogen evolution catalyst prepared by the invention is wrapped on the rod-shaped conductive substrate in a spiral shape, the spiral structure ensures that the catalyst does not have the phenomenon of reducing the catalytic activity due to the fact that clusters are sintered, and meanwhile, the spiral surface structure enlarges the contact area of the catalyst and provides a considerable number of active sites, so that the catalyst has excellent hydrogen evolution activity.
(2) The hydrogen evolution catalyst prepared by the invention and Mo2Compared with the traditional commercialized platinum-carbon catalyst, the catalyst C has greatly improved hydrogen evolution performance, greatly reduced platinum loading capacity and reduced cost, and provides a feasible scheme for reducing the high cost of the hydrogen production by water electrolysis.
(3) The invention prepares spiral ultra-low platinum load Mo2The catalyst C can obtain an integrated electrode containing effective catalytic components, has simple preparation process and convenient use, can be directly used as a working electrode to participate in water electrolysis reaction, and is suitable for wide application in the field of hydrogen production by water electrolysis.
Drawings
FIG. 1 is a spiral of ultra-low platinum loading Mo prepared in example 1 of this invention2C, scanning electron microscope photo of the catalyst;
FIG. 2 is a spiral of ultra-low platinum loading Mo prepared in example 1 of the invention2XRD spectrogram of the catalyst C;
FIG. 3 is a spiral of ultra-low platinum Mo loadings prepared in example 1 of this invention2C thermogravimetric result graph of catalyst;
FIG. 4 is a spiral of ultra-low platinum loading Mo prepared in example 1 of this invention2C catalyst and spiral Mo2C hydrogen evolution performance of the catalyst is compared with a graph;
FIG. 5 is a spiral of ultra-low platinum loading Mo prepared in example 2 of this invention2XRD spectrogram of the catalyst C;
FIG. 6 is a spiral of ultra-low platinum loading Mo prepared in example 2 of this invention2C catalyst and spiral Mo2C hydrogen evolution performance of the catalyst is compared with a graph;
FIG. 7 is a spiral of ultra-low platinum loading Mo prepared in example 3 of this invention2XRD spectrogram of the catalyst C;
FIG. 8 is a spiral of ultra-low platinum loading Mo prepared in example 3 of this invention2C catalyst and spiral Mo2Comparative graph of hydrogen evolution performance of catalyst C.
FIG. 9 is a spiral of ultra-low platinum loading Mo prepared in example 4 of this invention2XRD spectrogram of the catalyst C;
FIG. 10 is a spiral of ultra-low platinum loading Mo prepared in example 4 of this invention2C catalyst and spiral Mo2Hydrogen evolution performance of the catalyst C is compared.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the examples below, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
The embodiment provides a spiral ultra-low platinum loading Mo applicable to the hydrogen evolution reaction of electrolytic water2C, the preparation method of the catalyst is as follows.
(1) The obtained carbon cloth material was cut into a size of 1.0cm × 2.0 cm. Ultrasonically cleaning the mixture by using ethanol with the purity of 95% and deionized water respectively, and drying the mixture for later use.
(2) Measuring 150mL ammonium molybdate solution with concentration of 10mmol/L as electrolyte, fixing carbon cloth as working electrode with polytetrafluoroethylene electrode clamp, immersing in ammonium molybdate electrolyte, using carbon rod as counter electrode to form double-electrode electrolytic cell, and performing constant current cathodic electrodeposition at 4mA/cm2The electrodeposition time is 30min under the current density of (1), and then the working electrode is cleaned by deionized water and dried to obtain the spiral MoO2And (3) precursor.
(3) The spiral MoO prepared in the step (2) is used2Putting the precursor into a clean corundum square boat at an angle of 45 degrees to ensure that two sides of the carbon cloth can be fully contacted with reaction gas, putting the corundum square boat in a tubular furnace, and introducing Ar/H (argon/hydrogen) at room temperature2Mixing gas for 30min to ensure that the air in the tube furnace is fully exhausted, and then Ar/H2The flow rate of the mixed gas is adjusted to 150sccm, the temperature is raised to 900 ℃ at the temperature raising rate of 5 ℃/min, and then Ar/H is maintained2Keeping the flow rate of the mixed gas constant for 80min, and then introducing CH4Controlling the flow rate of gas to be 50sccm, keeping the temperature for 60min, cooling to room temperature at the speed of 5 ℃/min, taking out the carbon cloth from the tubular furnace, washing with deionized water, and drying to obtain the spiral Mo2And (C) a catalyst.
(4) The spiral Mo prepared in the step (3)2The catalyst C was sandwiched by a Teflon electrode holder as a working electrode, a clean bright platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode, and 150mL of 0.5mol/L H2SO4As an electrolyte, a three-electrode electrolytic cell system is built, a cyclic voltammetry scanning method is adopted for processing (0 to-0.5V vs. RHE), the scanning rate is 50mV/s, the processing time is 12h, and the spiral ultra-low platinum-carrying Mo can be obtained after washing and drying by deionized water2And C, a catalyst.
The spiral ultra-low platinum loading Mo obtained by the embodiment2C, the catalyst was analyzed by scanning electron microscopy, and as shown in fig. 1, the catalyst was tightly and uniformly wound in a spiral shape on the carbon fibers of the carbon cloth.
The spiral ultra-low platinum loading Mo obtained in this example2XRD pattern analysis of the catalyst C, as shown in FIG. 2, it can be seen that the catalyst prepared in this example has a composition of β -Mo2C, and no other miscellaneous peaks, demonstrates MoO2The precursor has been completely converted into Mo2C, and the main component of the whole catalyst is Mo2C。
The spiral ultra-low platinum loading Mo obtained in this example2Performing Thermogravimetric (TG) analysis on the catalyst C, and simultaneously performing Thermogravimetric (TG) analysis on the catalyst C and the spiral Mo prepared in the step (3)2C, comparing the catalysts, and comparing the TG results of the catalysts to obtain the content of the platinum in the catalyst. As shown in FIG. 3, in example 1, carbon was removed by high-temperature treatment in air, and each metal element was oxidized to leave PtO2/MoO3About 0.65 wt% of the electrode, slightly higher than Mo after the same treatment2C catalyst (0.63 wt%), indicating PtO2The mass fraction of the electrode was about 0.02 wt%, further calculated to give a platinum loading of 2.96 μ g/cm in example 12And Pt accounts for 0.017 wt% of the whole electrode, so that the spiral ultralow platinum catalyst prepared in the example 1 is extremely low in platinum loading, and meets the requirement of the ultralow platinum loading catalyst.
Spiral ultra-low platinum-loading Mo prepared by using the method2C catalyst is used for testing the hydrogen evolution reaction activity and is matched with the Mo obtained in the step 3)2C catalyst (marked as spiral Mo2C catalyst) were compared for activity.
The spiral ultra-low platinum loading Mo obtained in this example2The C catalyst is used as a working electrode, the carbon rod is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and 0.5mol/L H is adopted2SO4The linear voltammetry scan test was performed as an electrolyte, and the test results are shown in fig. 4, and it can be seen that the spiral shape prepared in this exampleUltra-low platinum loading Mo2The hydrogen evolution activity of the C catalyst is far better than that of spiral Mo2RHE, the initial potential of the catalyst is only 24.27mV vs, and the current density reaches 10mA/cm2The potential required was only 74.20mV vs. RHE.
Example 2
Spiral ultralow platinum loading Mo capable of being applied to electrolytic water evolution hydrogen reaction2C, the preparation method of the catalyst is as follows.
(1) The carbon cloth material was cut into a size of 1.0cm × 2.0 cm. Ultrasonically cleaning the mixture by using ethanol with the purity of 95% and deionized water respectively, and drying the mixture for later use.
(2) Measuring 100mL ammonium molybdate solution with concentration of 10mmol/L as electrolyte, fixing carbon cloth as working electrode with polytetrafluoroethylene electrode clamp, immersing in ammonium molybdate electrolyte, using carbon rod as counter electrode to form double-electrode electrolytic cell, and performing constant current cathodic electrodeposition at 6mA/cm2The electrodeposition time is 30min under the current density of (1), and then the working electrode is cleaned and dried by deionized water to obtain the spiral MoO2And (3) precursor.
(3) The spiral MoO prepared in the step 2) is added2Putting the precursor into a clean corundum square boat at an angle of 45 degrees to ensure that two sides of the carbon cloth can be fully contacted with reaction gas, putting the corundum square boat in a tubular furnace, and introducing Ar/H (argon/hydrogen) at room temperature2Mixing gas for 30min to ensure that the air in the tube furnace is fully exhausted, and then Ar/H2The flow rate of the mixed gas is 150sccm, the temperature is raised to 900 ℃ at a temperature raising rate of 5 ℃/min, and then Ar/H is maintained2Keeping the flow rate of the mixed gas constant for 80min, and introducing CH4Controlling the flow rate of gas to be 50sccm, keeping the temperature for 120min, cooling to room temperature at the speed of 5 ℃/min, taking out the carbon cloth from the tubular furnace, washing with deionized water, and drying to obtain the spiral Mo2And C, a catalyst.
(4) The spiral Mo prepared in the step (3)2The catalyst C was sandwiched by a Teflon electrode holder as a working electrode, a clean bright platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode, 100ml of 0.5mol/L H2SO4As electricityDecomposing the solution, building a three-electrode electrolytic cell system, treating (0-0.5V vs. RHE) by cyclic voltammetry at a scanning rate of 50mV/s for 12h, washing with deionized water, and drying to obtain spiral Mo with ultralow platinum loading2And C, a catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2XRD analysis of the C catalyst was conducted, and as shown in FIG. 5, it can be seen that the catalyst prepared in this example had a composition of β -Mo2C, and no other miscellaneous peaks, demonstrates MoO2The precursor has been completely converted into Mo2C, and the main component of the whole catalyst is Mo2C。
The spiral ultra-low platinum loading Mo obtained using this example2C catalyst is tested for hydrogen evolution reaction activity and is combined with spiral Mo2C, comparing the activity of the catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2The C catalyst is used as a working electrode, the carbon rod is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and 0.5mol/L H is adopted2SO4The linear voltammetry scanning test is carried out as the electrolyte, the test result is shown in fig. 6, and it can be seen that the hydrogen evolution activity of the catalyst prepared by the example is far better than that of the spiral Mo2The initial potential of the C catalyst is only 16.99mV vs. RHE, and the current density reaches 10mA/cm2The potential required was only 72.55mV vs. RHE.
Example 3
Spiral ultralow platinum loading Mo capable of being applied to electrolytic water evolution hydrogen reaction2C, the preparation method of the catalyst is as follows.
(1) The carbon cloth material was cut into a size of 1.0cm × 2.0 cm. Ultrasonically cleaning the mixture by using ethanol with the purity of 95% and deionized water respectively, and drying the mixture for later use.
(2) Measuring 150mL of ammonium molybdate solution with the concentration of 5mmol/L as electrolyte, fixing carbon cloth as a working electrode by using a polytetrafluoroethylene electrode clamp, immersing the working electrode in the ammonium molybdate electrolyte, and using carbon paper as a counter electrode to form a double-electrode electrolytic cell, and adopting a constant-current cathodic electrodeposition mode at 4mA/cm2At a current density of (2), at the time of electrodepositionThe time is 20min, and then the working electrode is cleaned by deionized water and dried to obtain the spiral MoO2And (3) precursor.
(3) The spiral MoO prepared in the step (2) is used2Putting the precursor into a clean corundum square boat at an angle of 45 degrees to ensure that two sides of the carbon cloth can be fully contacted with reaction gas, putting the corundum square boat in a tubular furnace, and introducing Ar/H (argon/hydrogen) at room temperature2Mixing gas for 30min to ensure that the air in the tube furnace is fully exhausted, and then Ar/H2The flow rate of the mixed gas is 100sccm, the temperature is raised to 800 ℃ at the temperature raising rate of 5 ℃/min, and then Ar/H is kept2Keeping the flow rate of the mixed gas constant for 60min, and then introducing CH4Controlling the flow rate of gas to be 50sccm, keeping the temperature for 60min, then cooling to room temperature at the speed of 10 ℃/min, taking out the carbon cloth from the tubular furnace, washing with deionized water, and drying to obtain the spiral Mo2And C, a catalyst.
(4) The spiral Mo prepared in the step (3)2The catalyst C was sandwiched by a Teflon electrode holder as a working electrode, a clean bright platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode, and 150mL of 0.5mol/L H2SO4And (2) building a three-electrode electrolytic cell system as an electrolyte, treating the solution by adopting a cyclic voltammetry scanning method (0 to-0.5V vs. RHE), wherein the scanning rate is 50mV/s, the treatment time is 14h, and washing and drying the solution by using deionized water to obtain the spiral ultralow platinum catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2XRD pattern analysis of the catalyst C, as shown in FIG. 7, it can be seen that the catalyst prepared in this example has a composition of β -Mo2C, and no other miscellaneous peaks, demonstrates MoO2The precursor has been completely converted into Mo2C。
Spiral ultra-low platinum-loading Mo prepared by using the method2C catalyst is tested for hydrogen evolution reaction activity and is combined with spiral Mo2C, comparing the activity of the catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2C catalyst as working electrode, carbon rod as counter electrode, and saturated calomel electrode as referenceElectrode, using 0.5mol/L H2SO4The test results of the linear voltammetry scan test performed as the electrolyte are shown in fig. 8, and it can be seen that the hydrogen evolution activity of the hydrogen evolution catalyst prepared in the example is far better than that of the spiral Mo2RHE, the initial potential of the catalyst is only 24.62mV vs, and the current density reaches 10mA/cm2The potential required was only 91.66mV vs. RHE.
Example 4
The embodiment provides a spiral ultra-low platinum loading Mo applicable to the hydrogen evolution reaction of electrolytic water2C, the preparation method of the catalyst is as follows.
(1) The commercially available carbon cloth material was cut to a size of 1.0cm × 2.0 cm. Ultrasonically cleaning the mixture by using ethanol with the purity of 95% and deionized water respectively, and drying the mixture for later use.
(2) Measuring 150mL ammonium molybdate solution with concentration of 10mmol/L as electrolyte, fixing carbon cloth as working electrode with polytetrafluoroethylene electrode clamp, immersing in ammonium molybdate electrolyte, using carbon rod as counter electrode to form double-electrode electrolytic cell, and performing constant current cathodic electrodeposition at 8mA/cm2At the current density of (3), the electrodeposition time is 10min, and then the working electrode is cleaned by deionized water and dried to obtain the spiral MoO2And (3) precursor.
(3) The spiral MoO prepared in the step (2) is used2Putting the precursor into a clean corundum square boat at an angle of 45 degrees to ensure that two sides of the carbon cloth can be fully contacted with reaction gas, putting the corundum square boat in a tubular furnace, and introducing Ar/H (argon/hydrogen) at room temperature2Mixing gas for 30min to ensure that the air in the tube furnace is fully exhausted, and then Ar/H2The flow rate of the mixed gas is adjusted to 150sccm, the temperature is raised to 1000 ℃ at the temperature raising rate of 5 ℃/min, and then Ar/H is maintained2Keeping the flow rate of the mixed gas constant for 80min, and then introducing CH4Controlling the flow rate of gas at 50sccm, keeping the temperature for 50min, cooling to room temperature at the rate of 5 ℃/min, taking out the carbon cloth from the tubular furnace, washing with deionized water, and drying to obtain spiral Mo2And C, a catalyst.
(4) The spiral Mo prepared in the step (3)2Polytetramethylene for C catalystA fluoroethylene electrode holder as a working electrode, a cleaned bright platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode, and 150mL of 0.5mol/L H2SO4As an electrolyte, a three-electrode electrolytic cell system is built, a cyclic voltammetry scanning method is adopted for processing (0 to-0.5V vs. RHE), the scanning rate is 80mV/s, the processing time is 8h, and the spiral ultra-low platinum-carrying capacity Mo can be obtained after washing and drying by deionized water2And C, a catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2XRD pattern analysis of the catalyst C, as shown in FIG. 9, it can be seen that the catalyst prepared in this example has a composition of β -Mo2C, and no other miscellaneous peaks, demonstrates MoO2The precursor has been completely converted into Mo2C。
Spiral ultra-low platinum-loading Mo prepared by using the method2C catalyst is tested for hydrogen evolution reaction activity and is combined with spiral Mo2C, comparing the activity of the catalyst.
The spiral ultra-low platinum loading Mo obtained in this example2The C catalyst is used as a working electrode, the carbon rod is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and 0.5mol/L H is adopted2SO4The test results of the linear voltammetry scan test performed as the electrolyte are shown in fig. 10, and it can be seen that the hydrogen evolution activity of the hydrogen evolution catalyst prepared in the example is far better than that of the spiral Mo2The initial potential of the C catalyst is only 23.65mV vs. RHE, and the current density reaches 10mA/cm2The potential required was only 83.99mV vs. RHE.
Example 5
The embodiment provides a spiral ultra-low platinum loading Mo applicable to the hydrogen evolution reaction of electrolytic water2C, the preparation method of the catalyst is as follows.
(1) The obtained carbon cloth material was cut into a size of 1.0cm × 2.0 cm. Ultrasonically cleaning the mixture by using ethanol with the purity of 95% and deionized water respectively, and drying the mixture for later use.
(2) Measuring 150mL ammonium molybdate solution with concentration of 10mmol/L as electrolyte, fixing carbon cloth as working electrode with polytetrafluoroethylene electrode clamp, and immersing in ammonium molybdate electrolyteThe carbon rod is used as a counter electrode to form a double-electrode electrolytic cell, and a constant-current cathodic electrodeposition mode is adopted, wherein the concentration of the carbon rod is 2mA/cm2At the current density of (3), the electrodeposition time is 50min, and then the working electrode is cleaned by deionized water and dried to obtain the spiral MoO2And (3) precursor.
(3) The spiral MoO prepared in the step (2) is used2Putting the precursor into a clean corundum square boat at an angle of 45 degrees to ensure that two sides of the carbon cloth can be fully contacted with reaction gas, putting the corundum square boat in a tubular furnace, and introducing Ar/H (argon/hydrogen) at room temperature2Mixing gas for 30min to ensure that the air in the tube furnace is fully exhausted, and then Ar/H2The flow rate of the mixed gas is adjusted to 150sccm, the temperature is raised to 700 ℃ at the temperature raising rate of 5 ℃/min, and then Ar/H is maintained2Keeping the flow rate of the mixed gas constant for 80min, and introducing CH4Controlling the flow rate of the gas to be 50sccm, keeping the temperature for 100min, then cooling to room temperature at the speed of 5 ℃/min, taking the carbon cloth out of the tubular furnace, washing with deionized water, and drying to obtain the spiral Mo2And C, a catalyst.
(4) The spiral Mo prepared in the step (3)2The catalyst C was sandwiched by a Teflon electrode holder as a working electrode, a clean bright platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode, and 150mL of 0.5mol/L H2SO4As an electrolyte, a three-electrode electrolytic cell system is built, a cyclic voltammetry scanning method is adopted for processing (0 to-0.5V vs. RHE), the scanning rate is 20mV/s, the processing time is 14h, and the spiral ultra-low platinum-carrying Mo can be obtained after washing and drying by deionized water2And C, a catalyst.
From the above, the preparation method of the invention has simple process, and the prepared catalyst and Mo are2Compared with the traditional commercialized platinum-carbon catalyst, the catalyst C has greatly improved hydrogen evolution performance, greatly reduced platinum loading capacity and reduced cost, and provides a feasible scheme for reducing the high cost of the hydrogen production by water electrolysis. In addition, the catalyst is an integrated electrode containing effective catalytic components, can be used as a working electrode to participate in water electrolysis reaction, and is suitable for wide application in the field of hydrogen production by water electrolysis。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Spiral ultralow platinum loading Mo2The preparation method of the catalyst C is characterized by comprising the following steps:
s1: spiral MoO2Preparing a precursor: depositing on a rod-shaped conductive substrate by adopting an electrodeposition technology to obtain spiral MoO2A precursor;
s2: spiral Mo2C, preparation of a catalyst: the spiral MoO2Precursor in Ar/H2Keeping the temperature of 700-1000 ℃ for 50-100 min in the mixed gas atmosphere, then introducing hydrocarbon gas, and cooling to obtain spiral Mo2C, a catalyst;
s3: spiral ultra-low platinum loading Mo2C, preparation of a catalyst: in the spiral Mo2Electroplating platinum on the C catalyst, washing and drying to obtain the spiral ultralow platinum-loading Mo2C, a catalyst;
the spiral ultra-low platinum loading Mo2The platinum loading in the C catalyst is not higher than 15 mu g/cm2。
2. The method according to claim 1, wherein the electrodeposition in S1 is performed by galvanostatic electrodeposition and is performed in a two-electrode electrolytic cell.
3. The preparation method according to claim 2, wherein the working electrode selected by the double-electrode electrolytic cell is carbon cloth, the counter electrode is a carbon rod, carbon cloth or carbon paper, and the electrolyte is ammonium molybdate solution.
4. The method of claim 2, wherein the galvanostatic cathode is used as a cathodeThe external constant current of the deposition is 2-8 mA/cm2The electrodeposition time is 10-50 min.
5. The method according to claim 1, wherein S2Ar/H2H in mixed gas atmosphere2The volume fraction of (A) is 2-20%.
6. The method of claim 1, wherein the step of electroplating S3 with platinum is performed using a three-electrode electrolytic cell.
7. The method as claimed in claim 6, wherein the working electrode of the three-electrode electrolytic cell is spiral Mo2C catalyst, counter electrode of platinum and electrolyte of H2SO4And (3) solution.
8. The method for preparing the platinum alloy as claimed in claim 7, wherein the method for electroplating platinum is cyclic voltammetry scanning electroplating, and the scanning voltage is 0 to-0.7Vvs. RHE, the scanning speed is 20-100 mV/s, and the electroplating time is 8-14 h.
9. Spiral ultralow platinum loading Mo2The catalyst C is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The helical ultra-low platinum loading Mo of claim 92The application of the C catalyst in the field of electrocatalytic hydrogen evolution.
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