CN111266109A - Ru-WOxNanowire HER catalyst and preparation method thereof - Google Patents
Ru-WOxNanowire HER catalyst and preparation method thereof Download PDFInfo
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- CN111266109A CN111266109A CN201811474129.0A CN201811474129A CN111266109A CN 111266109 A CN111266109 A CN 111266109A CN 201811474129 A CN201811474129 A CN 201811474129A CN 111266109 A CN111266109 A CN 111266109A
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- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000003054 catalyst Substances 0.000 title description 41
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 239000000126 substance Substances 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 27
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- 229910052707 ruthenium Inorganic materials 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
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- 239000000843 powder Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003657 tungsten Chemical class 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 3
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 238000011068 loading method Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
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- 229910000510 noble metal Inorganic materials 0.000 description 7
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
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- 239000007809 chemical reaction catalyst Substances 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
- B01J23/6527—Tungsten
-
- B01J35/33—
-
- B01J35/40—
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a Ru-WOxThe composite material comprises a carrier and Ru loaded on the surface of the carrier in the form of clusters, wherein the chemical formula of the carrier is WOxWherein x is more than or equal to 2 and less than or equal to 3, and the content of Ru in the composite material is 0.1-5 wt%.
Description
Technical Field
The invention relates to a cathode catalyst for an electrolytic water Hydrogen Evolution Reaction (HER) and a preparation method thereof, in particular to a WO cathode catalystxA nanowire loaded Ru elemental HER catalyst and a preparation method thereof.
Background
The shortage of fossil energy in the world, the continuous deterioration of ecological environment, frequent extreme climate and other problems cause high concern and worry of people, the search for novel alternative energy becomes an important sustainable development strategy, and the advantages of high energy density, no pollution and the like of hydrogen are considered to be novel energy with great potential. China clearly points out the target of future hydrogen energy development and brings out relevant policies and measures, but still has many scientific problems in the preparation and collection of hydrogen energy. The electrolyzed water is used as a very ideal hydrogen production method, but the current main electrocatalytic Hydrogen Evolution Reaction (HER) catalyst is noble metal Pt, the high price of the catalyst greatly increases the use cost, and the development of the hydrogen production industry by the electrolyzed water is limited. The search for inexpensive alternative catalysts and simple and low-cost process technology has become a hot issue of research in this direction.
At present, the electrolytic water catalysts reported at home and abroad are mainly divided into precious metals and non-precious metals, and although the price of the non-precious metal catalysts (such as Co, Ni, Cu and the like) is low, the general problems are that the catalytic reaction activity is not enough, higher overpotential is often needed in the catalytic reaction, and the reaction stability is not as good as that of the precious metal catalysts; noble metal catalysts (such as Pt, Pd, Ph, Ru and the like) have high electrocatalytic hydrogen evolution activity and good stability, but are expensive, and the use cost is increased.
Disclosure of Invention
In consideration of various aspects, the invention aims to solve the problems that the prior HER non-noble metal catalyst has insufficient catalytic activity, the cost is increased due to high use content of noble metal catalyst, the preparation method is complicated and is not suitable for large-scale commercial use, and provides the noble metal Ru loaded WO with low costxA nanowire composite catalyst and a preparation method thereof.
In one aspect, the invention provides a composite material, which comprises a carrier and Ru loaded on the surface of the carrier in the form of clusters, wherein the carrier has a chemical formula of WOxX is more than or equal to 2 and less than or equal to 3, and the content of Ru in the composite material is 0.1-1.5 wt%.
The Ru-WO of the inventionxThe composite material is prepared by using WOxThe weak reducibility of the ruthenium source directly leads the ruthenium source to be in situAnd (4) reduction and formation. WOxThe powdery solid has a good linear structure, and is beneficial to loading of Ru clusters. In WOxThe carrier surface is modified with precious metal Ru with extremely low content, and can be used as HER catalyst. The content of Ru is 0.1-5wt%, and the catalyst material is a noble metal supported catalyst material with extremely low content, can simultaneously give consideration to catalytic performance and cost inhibition, has great large-scale commercial use value, and can effectively promote the development of hydrogen economy. Ru and WOxThe carrier forms a synergistic catalysis effect, and shows high HER catalytic activity and stability. The overpotential of the composite material of one embodiment of the invention is only 45mV under the current density of 10mA cm < -2 >, the activity is equivalent to 20% of Pt/C, and the composite material still maintains more than 80% of activity under the continuous working condition of 10 hours; its high catalytic activity and high stability mainly result from the synergistic catalytic action between the Ru and WOx carriers.
Preferably, the content of Ru in the composite material is 2-4 wt%.
Preferably, the carrier is shaped like a sea urchin-shaped nanowire which is mainly obtained by alcoholysis reaction and is in a divergent linear shape, the diameter of the nanowire is 5-10nm, and the length of the nanowire is 50-100 nm. Thereby exposing more active sites relative to conventional particulate and bulk materials.
Preferably, the size of Ru is 1-2 nm.
On the other hand, the invention also provides a preparation method of the composite material, which is characterized by comprising the following steps:
mixing tungsten salt and a first solvent to obtain a mixed solution, carrying out heat treatment on the mixed solution at the temperature of 150-200 ℃, centrifuging and drying to obtain WOxA powdered solid;
subjecting said WO toxMixing the powdery solid with a second solvent and a ruthenium source, stirring for 12-15 hours, and then centrifuging and drying the obtained suspension to obtain precursor powder;
and annealing the precursor powder in a reducing atmosphere to obtain the composite material.
In the present invention, WO is first prepared by hydrothermal reactionxA powdered solid. The WOxThe powdery solid isWO with weak reducibilityxA nanowire. Preferably may be a deep blue WO2.72And (3) powder. Due to WOxIn which both the 5-and 6-valent W, and the pentavalent W is reductive and tends to react with oxidizing substances, makes WOxItself has weak reducibility; then by using WO at room temperaturexThe ruthenium source is directly reduced in situ to form cluster-shaped Ru by the weak reducibility of the ruthenium source, and the Ru-WO is obtainedxA composite material. The method has mild preparation conditions and is easy to operate.
The tungsten salt can be at least one of tungsten hexachloride, tungsten hexacarbonyl and tungsten tetrachloride; the first solvent can be at least one of ethanol, isopropanol and ethylene glycol; the ratio of the tungsten salt to the first solvent may be (50-100) mg: (80-100) ml.
The time for the heat treatment may be 10 to 20 hours.
The ruthenium source can be at least one selected from ruthenium chloride solution with the concentration of 1-5g/L and ruthenium nitrate (ruthenium nitrate with the concentration of 1-5 g/L); said WOxThe ratio of the powdered solid to the ruthenium source may be (100-500) mg: (0.1-1.5) ml.
The ruthenium chloride solution is RuCl4The concentration of the solution prepared by the solid and the water is 1-5 g/L.
The second solvent may be at least one of water, isopropanol, ethylene glycol; the ratio of the second solvent to the ruthenium source may be (100-200) ml: (0.1-1.5) ml.
Preferably, the WO is appliedxAnd (3) uniformly mixing the powdery solid and the second solvent, adding a ruthenium source into the mixture, stirring for 12-15 hours, and centrifuging and drying the obtained suspension to obtain precursor powder.
The annealing temperature can be 200-400 ℃, and the heat preservation time can be 2-4 hours. The annealing can change all the Ru on the surface into stable clusters, and the stability of the load can be improved to a certain extent.
The reducing atmosphere may be H2、H2Mixed gas with Ar, CO or CH4And the like. That is, in the present invention, the reducing atmosphere may beComprising a reducing gas and an inert gas. In the presence of reducing gases and inert gases, e.g. H2In the case of/Ar, the volume ratio of the reducing gas to the inert gas may be (5% to 20%): (95% -80%).
Drawings
FIG. 1 shows Ru-WO prepared in example 1 of the present invention2.72An XRD pattern of the composite material;
FIG. 2(a) shows WO prepared in example 1 of the present invention2.72SEM photograph of the nanowires;
FIG. 2(b) shows WO prepared in example 1 of the present invention2.72SEM photograph of the nanowires;
FIG. 2(c) shows WO prepared in example 1 of the present invention2.72TEM photograph of the nano-wire;
FIG. 2(d) shows Ru loading of 2 wt% Ru-WO prepared in example 1 of the invention2.72SEM photograph of the composite;
FIG. 2(e) shows Ru loading of 2 wt% Ru-WO prepared in example 1 of the invention2.72TEM photograph of the composite material;
FIG. 2(f) shows Ru loading of 2 wt% Ru-WO prepared in example 1 of the invention2.72HAADF photographs and elemental profiles of composite materials;
FIG. 3(a) shows different Ru-loading WO prepared in various examples of the invention2.72HER Properties of the composite (WR 1: 5wt% Ru-WO)2.72；WR2：4wt％Ru-WO2.72；WR3：2wt％Ru-WO2.72；WR4：0.1wt％Ru-WO2.72)；
FIG. 3(b) shows 2 wt% Ru-WO prepared in example 1 of the present invention2.72Catalyst and WO not carrying Ru2.72HER curves for commercial 20 wt% Pt/C and 5wt% Ru/C catalysts;
FIG. 3(c) shows different contents of Ru-WO prepared in the examples of the present invention2.72The current density of the composite catalyst and other comparative materials is 10mA cm-2An overpotential of (d);
FIG. 3(d) shows 2 wt% Ru-WO prepared in example 1 of the present invention2.72HER curves before and after 2000 cycles of composite catalyst cycling (large graph in fig. 3 (d)), and stability curve for 10 hours of continuous operation (small graph in fig. 3 (d)).
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to illustrate and not to limit the present invention.
The invention provides a novel Ru-loaded WOxA nanowire composite material and a preparation method thereof. The Ru-WOxThe composite material can be used as a catalyst material for electrocatalytic Hydrogen Evolution Reaction (HER), and the Ru-WOxComposite materials are described in WOx(x is 2-3) the surface of the material is loaded with atoms Ru, Ru and WOxThe synergistic catalytic action among the nanowire substrates enables the novel catalyst material to show HER catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst; the catalyst material has low Ru consumption (less than 5 wt%), greatly reduced catalyst cost and high economic benefit. The preparation process is that firstly, WO is prepared by hydrothermal reactionxNanowires, then by using WO at room temperaturexDirectly reducing ruthenium chloride in situ to form clusters by weak reducibility of the ruthenium chloride to obtain Ru-WOxA composite material. The method has mild preparation conditions and is easy to operate.
Ru-WO of the inventionxThe composite material comprises a carrier and Ru loaded on the surface of the carrier in the form of clusters, wherein the chemical formula of the carrier is WOxAnd x is 2-3, preferably 2 ≦ x < 3. For example, when x is 2.72, WO2.72 is structurally stable with the crystalline form intact (fig. 1). The Ru-WOxThe content of Ru in the composite material can be 0.1 to 5 wt.%, preferably 2 to 4 wt.%. For example, the highest activity is obtained at a Ru content of 2 wt.%.
Hereinafter, preparation of the Ru-loaded WO of the invention is exemplifiedxA preparation method of a nanowire composite material.
Firstly, a tungsten salt and a first solvent are uniformly mixed to obtain a mixed solution. The tungsten salt can be tungsten hexachloride, tungsten hexacarbonyl, tungsten tetrachloride, and the like. The first solvent may be ethanol, isopropanol, ethylene glycol, or the like. The ratio of the tungsten salt to the first solvent may be (50-100) mg: (80-100) ml. The mixing may be performed by stirring, and may be performed at room temperature.
Then, after the obtained mixed solution is subjected to hydrothermal reaction, the obtained suspension is centrifuged and dried to obtain a powdery solid. The reaction temperature can be 150-200 ℃, preferably 180-200 ℃, and the time can be 10-20 hours, and the obtained powdery solid is WOxThe nano wire is blue or deep blue, the diameter of the nano wire is 5-10nm, and the length of the nano wire is 50-100 nm. For example, as can be seen from FIG. 1, WO2.72The XRD peak position of the powdery solid is obvious and the peak is higher, which shows that WO2.72Has good crystallization property and is beneficial to the loading of Ru. Can be naturally cooled and taken out, and the obtained suspension is centrifugally dried to obtain deep blue WOxA nanowire. The drying may be performed using a freeze dryer.
Then, the obtained WOxAnd mixing the powdery solid with a second solvent and a ruthenium source, stirring for 12-15 hours, and centrifuging and drying the obtained suspension to obtain precursor powder. Thus, WO to be preparedxNanowires as carriers for Ru atoms, using WOxThe weak reducibility of the ruthenium source per se reduces the ruthenium source from the solution and successfully and uniformly loads the ruthenium source to WOxOn the nanowire. The ruthenium source may be selected from ruthenium chloride solution, ruthenium nitrate, etc. at a concentration of 1-5g/L, WOxThe ratio of the powdered solid to the ruthenium source may be (100-500) mg: (0.1-1.5) ml, and the reaction can be carried out sufficiently in this range. For example, the ruthenium chloride solution may be prepared from RuCl4 and water at a concentration of 0.1-0.5 g/L. The second solvent may be water, isopropanol, ethylene glycol, or the like. The ratio of the second solvent to the ruthenium source may be (100-200) ml: (0.1-1.5) ml. WOxThe order of mixing the powdered solid with the second solvent, the ruthenium source may be WOxThe powdered solid is mixed with a second solvent and the ruthenium source is added thereto. The ruthenium source can be slowly added dropwise to WOxThe mixture of the powdered solid and the second solvent is stirred vigorously (for example, by a magnetic stirrer), and the dropping speed can be 0.1mL/min to 0.2mL/min, so that Ru and WO can be addedxThe reaction was sufficient to increase the number of crystallization sites and slow the crystallization rate. Can be combined with the above-mentionedThe suspension is washed several times by centrifugation and subsequently dried in a freeze dryer. Ru-WO with different loading concentrations is obtained by regulating the content of a ruthenium source (such as ruthenium chloride)xThe composite material controls the loading amount of Ru on the surface.
Then, annealing the obtained precursor powder in a reducing atmosphere to obtain Ru-WOxA composite material. The annealing temperature can be 200-400 ℃, preferably 200-300 ℃, and the heat preservation time can be 2-4 hours. The Ru can be stably loaded on the carrier through annealing and is not easy to fall off. The reducing atmosphere may be H2、CO、CH4Or a mixed gas of at least one of them with Ar. That is, in the present invention, the reducing atmosphere may contain a reducing gas and an inert gas. In the presence of reducing gases and inert gases, e.g. H2In the case of/Ar, the volume ratio of the reducing gas to the inert gas may be (5% to 20%): (95% -80%).
Ru-WO prepared according to the above processxThe composite catalyst material is linear, the diameter of the linear is 5-10nm, and the length of the linear is 50-100 nm. WOxThe surface of the nanowire is loaded with Ru clusters with extremely low content, and the loading amount is 0.1-5 wt%. Ru supported in cluster form on WOxThe surface of the nanowire is greatly exposed to more active sites. The size of the cluster Ru is 1-2 nm. Ru and WOxThe carrier forms a synergistic catalysis effect, and shows high HER catalytic activity and stability.
The invention has the advantages that:
a very low (0.5-1.5 wt%) content of noble metal Ru loaded WO is proposedx(x ═ 2-3) nanowire composite electrocatalytic hydrogen evolution reaction catalyst material;
using WOxThe Ru is reduced by the weak reducibility of the material, so that effective load is realized, the method is simple, the condition is mild, and the operation is easy;
Ru-WO in the inventionxThe material is linear, has the diameter of 5-10nm and the length of about 50nm, has higher specific surface area and can expose more active sites compared with the traditional particle and block materials;
Ru-WO of the inventionxComplex catalysisAgent, Ru and WOxThe carrier forms a synergistic catalysis effect, and shows high HER catalytic activity and stability.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
According to the technical scheme and the process flow of the invention, firstly, WO is prepared2.72Dissolving 100mg of tungsten hexachloride in 80mL of absolute ethanol solution, stirring uniformly at room temperature, then placing in an 80mL reaction kettle, preserving heat at 150 ℃ for 10 hours, carrying out centrifugal separation and washing on the obtained suspension, and then drying in a freeze dryer to obtain dark blue powder;
then weighing 100mg of dark blue powder, adding 100mL of deionized water, continuously stirring until the mixture is uniform, and then slowly dropwise adding 0.5mL of 0.5gmL-1Ruthenium chloride solution, with vigorous stirring, using WO2.72Reducing Ru from the solution by virtue of weak reducibility, centrifugally separating and washing the obtained suspension for multiple times, and then drying in a freeze dryer; placing the dried powder under reducing atmosphere (H)2Ar) heating at 200 ℃ for 2 hours to obtain the final product Ru-WO2.72A nanowire composite.
Ru-WO prepared according to the above process2.72The composite catalyst material was linear in its entirety, with a wire diameter of 5-10nm and a length of about 50nm (as shown in fig. 2(a) -2 (c)), where the Ru loading was 2 wt%, which was measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES). The material is in N2The saturated 1M KOH solution shows excellent electro-catalytic hydrogen evolution performance, as shown in figure 3(a), andand exhibits good cycle stability and sustained operation stability as shown in fig. 3 (d).
Mixing the above Ru-WO2.72The nanowire composite material is used as a cathode catalyst for Hydrogen Evolution Reaction (HER) by electrolysis and is added in N2Testing of electrocatalytic hydrogen evolution performance in saturated 1M KOH solutions may include: the test was carried out using mainly the CHI760 electrochemical workstation; the test mainly adopts a three-electrode system and adopts Ru-WO2.72The powder and water are mixed and coated on glassy carbon electrode or other porous electrode (such as carbon cloth, nickel foil, etc., with concentration of 0.4-1mg/mL, and used as working electrode, suitable reference electrode and counter electrode are selected, graphite rod, carbon cloth, etc. are used as counter electrode, and Ag/AgCl, Hg/Hg, etc. can be used as counter electrode2SO4Etc. as reference electrodes. The electrolyte may contain K+、Na+Ionic solution to form a three-electrode system. The performance test adopts CV and LSV test methods, the scanning degree is 5mV/s, the test stability adopts a constant current method, the voltage is set to be 50mV, and the time is 10 hours.
Example 2
According to the process flow (same as example 1), weighing 100mg of dark blue powder, adding 100mL of deionized water, continuously stirring until the mixture is uniform, and then slowly dropwise adding 1.5mL of 0.5gmL-1Ruthenium chloride solution and vigorous stirring for 12 hours, using WO2.72Reducing Ru from the solution by virtue of weak reducibility, centrifugally separating and washing the obtained suspension for multiple times, and then drying in a freeze dryer; placing the dried powder under reducing atmosphere (H)2Ar) heating at 200 ℃ for 2 hours to obtain the final product Ru-WO2.72A nanowire composite.
Ru-WO prepared according to the above process2.72The composite catalyst material is in a linear shape as a whole, wherein the loading of Ru is 5wt%, and the material is in N2The saturated 1M KOH solution showed excellent electrocatalytic hydrogen evolution performance as shown in FIG. 3 a.
Example 3
According to the process flow (same as example 1), weighing 100mg of dark blue powder, adding 100mL of deionized water, continuously stirring until the mixture is uniform, and then slowly dropwise adding 1mL of deionized water with the concentration of0.5gmL-1Ruthenium chloride solution and vigorous stirring for 12 hours, using WO2.72Reducing Ru from the solution by virtue of weak reducibility, centrifugally separating and washing the obtained suspension for multiple times, and then drying in a freeze dryer; placing the dried powder under reducing atmosphere (H)2Ar) heating at 200 ℃ for 2 hours to obtain the final product Ru-WO2.72A nanowire composite.
Ru-WO prepared according to the above process2.72The composite catalyst material is in a linear shape as a whole, wherein the loading of Ru is 4wt%, and the material is in N2The saturated 1M KOH solution showed excellent electrocatalytic hydrogen evolution performance as shown in FIG. 3 a.
Example 4
According to the process flow (same as example 1), weighing 100mg of dark blue powder, adding 100mL of deionized water, continuously stirring until the mixture is uniform, and then slowly dropwise adding 0.5mL of 5g mL-1Ruthenium chloride solution and vigorous stirring for 12 hours, using WO2.72Reducing Ru from the solution by virtue of weak reducibility, centrifugally separating and washing the obtained suspension for multiple times, and then drying in a freeze dryer; placing the dried powder under reducing atmosphere (H)2Ar) heating at 200 ℃ for 2 hours to obtain the final product Ru-WO2.72A nanowire composite.
Ru-WO prepared according to the above process2.72The composite catalyst material is in a linear shape as a whole, wherein the loading of Ru is 2 wt%, and the material is in N2The saturated 1M KOH solution shows excellent electro-catalytic hydrogen evolution performance.
FIG. 1 shows Ru-WO prepared in example 1 of the present invention2.72Composite material and WO not loaded with Ru2.72XRD pattern of (a). As can be seen from FIG. 1, the material is essentially WO2.72The crystal structure of (2) and the peak position are obvious, which shows that the crystallization performance is good. FIG. 2(d) shows Ru loading of 2 wt% Ru-WO prepared in example 1 of the invention2.72SEM photograph of the composite material. As can be seen from FIG. 2(d), WO after loading2.72Still remaining linear. FIG. 2(e) shows the Ru loading prepared in inventive example 1In an amount of 2 wt% Ru-WO2.72TEM images of the composite material. As can be seen from FIG. 2(e), Ru is uniformly dispersed in WO2.72On a carrier. FIG. 2(f) shows Ru loading of 2 wt% Ru-WO prepared in example 1 of the invention2.72HAADF photograph of composite material and element distribution map. As can be seen from FIG. 2(f), the elements Ru, W and O are uniform.
Commercial 20 wt% Pt/C and 5wt% Ru/C catalysts were used as comparative examples 1, 2. FIG. 3(b) shows 2 wt% Ru-WO prepared in example 1 of the present invention2.72Catalyst and WO not carrying Ru2.72HER curves for commercial 20 wt% Pt/C and 5wt% Ru/C catalysts. As can be seen from FIG. 3(b), 2 wt% Ru-WO2.72The catalyst material showed HER catalytic activity comparable to a commercial 20 wt% Pt/C catalyst, 2 wt% Ru-WO at a current density of 10mA cm-22.72The overpotential of the catalyst is 45mV, and the 20% Pt/C is 32 mV. FIG. 3(c) shows different contents of Ru-WO prepared in examples 1-4 of the present invention2.72The current density of the composite catalyst and other comparative materials is 10mA cm-2An overpotential of (c). As can be seen from FIG. 3(c), the WO2.72 nanowire loaded with Ru has good activity and its overpotential is only 45 mV.
Example 5
According to the process flow (same as example 1), weighing 100mg of dark blue powder, adding 100mL of deionized water, continuously stirring until the mixture is uniform, and then slowly dropwise adding 0.1mL of 0.5gmL-1Ruthenium chloride solution and vigorous stirring for 12 hours, using WO2.72Reducing Ru from the solution by virtue of weak reducibility, centrifugally separating and washing the obtained suspension for multiple times, and then drying in a freeze dryer; placing the dried powder under reducing atmosphere (H)2Ar) heating at 200 ℃ for 2 hours to obtain the final product Ru-WO2.72A nanowire composite.
Ru-WO prepared according to the above process2.72The composite catalyst material is in a linear shape as a whole, wherein the loading of Ru is 0.1 wt%, and the material is in N2The saturated 1M KOH solution shows excellent electro-catalytic hydrogen evolution performance.
Claims (10)
1. A composite material is characterized by comprising a carrier and Ru loaded on the surface of the carrier in the form of clusters, wherein the carrier has a chemical formula of WOxWherein x is more than or equal to 2 and less than or equal to 3, and the content of Ru in the composite material is 0.1-5 wt%.
2. The composite material of claim 1, wherein the morphology of the carrier is nanowire-like, with a diameter of 5-10nm and a length of 50-100 nm.
3. The composite material according to claim 1 or 2, wherein the composite material has a Ru content of 2-4 wt%.
4. A method for preparing a composite material according to any one of claims 1 to 3, comprising:
mixing tungsten salt and a first solvent to obtain a mixed solution, carrying out heat treatment on the mixed solution at the temperature of 150-200 ℃, centrifuging and drying to obtain WOXA powdered solid;
subjecting said WO toXMixing the powdery solid with a second solvent and a ruthenium source, stirring for 12-15 hours, and then centrifuging and drying the obtained suspension to obtain precursor powder;
and annealing the precursor powder in a reducing atmosphere to obtain the composite material.
5. The production method according to claim 4, characterized in that the tungsten salt is at least one of tungsten hexachloride, tungsten hexacarbonyl, tungsten tetrachloride; the first solvent is at least one of ethanol, isopropanol and ethylene glycol; the ratio of the tungsten salt to the first solvent is (50-100) mg: (80-100) ml.
6. The method of claim 4 or 5, wherein the heat treatment is carried out for a period of 10 to 20 hours.
7. The article of any one of claims 4 to 6The preparation method is characterized in that the ruthenium source is at least one of ruthenium chloride solution with the concentration of 1-5g/L and ruthenium nitrate; said WOXThe ratio of powdered solid to the ruthenium source was (100-500) mg: (0.1-1.5) ml.
8. The production method according to any one of claims 4 to 7, wherein the second solvent is at least one of water, isopropyl alcohol, and ethanol; the ratio of the second solvent to the ruthenium source is (100-200) ml: (0.1-1.5) ml.
9. The method according to any one of claims 4 to 8, wherein the annealing temperature is 200 ℃ to 400 ℃, and the holding time is 2 to 4 hours.
10. The method according to any one of claims 4 to 9, wherein the reducing atmosphere is H2、H2Mixed gas with Ar, CO or CH4。
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