CN112760677B - Iridium-tungsten alloy nano material, preparation method thereof and application of iridium-tungsten alloy nano material as acidic oxygen evolution reaction electrocatalyst - Google Patents
Iridium-tungsten alloy nano material, preparation method thereof and application of iridium-tungsten alloy nano material as acidic oxygen evolution reaction electrocatalyst Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 19
- IGUHATROZYFXKR-UHFFFAOYSA-N [W].[Ir] Chemical compound [W].[Ir] IGUHATROZYFXKR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 title abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000001301 oxygen Substances 0.000 title abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 title description 19
- 239000010411 electrocatalyst Substances 0.000 title description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- 239000010937 tungsten Substances 0.000 claims abstract description 20
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkali metal salts Chemical class 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 14
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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 discloses an iridium-tungsten alloy nano material, a preparation method thereof and application of the iridium-tungsten alloy nano material as an acidic oxygen evolution reaction catalyst. The obtained nano material is loaded on carbon cloth and can be directly used as an electrode of an electrolytic cell, so that the problems of low diffusion rate, poor conductivity and the like caused by the use of a binder are avoided. Compared with the traditional IrO2The catalyst adopts the metal tungsten with rich content, low price and acid corrosion resistance as the main body structure, thereby greatly reducing the dosage of noble metal iridium and lowering the cost. And commercial IrO2Compared with the prior art, the alloy material has higher OER activity and stability and has higher industrial application prospect.
Description
Technical Field
The invention relates to the technical field of material chemistry and electrocatalysis, in particular to an iridium-tungsten alloy nano material, a preparation method thereof and application of the iridium-tungsten alloy nano material as an acidic oxygen evolution reaction electrocatalyst.
Background
Electrocatalysis is an energy conversion technology with wide prospect, and can convert electric energy which is difficult to store into energy in other forms, such as generating clean hydrogen energy by electrocatalysis water decomposition, and electrocatalysis carbon dioxide reduction (CO)2RR) to generate carbon energy, etc. Among these reactions, Oxygen Evolution Reaction (OER) plays an important role. Taking the water splitting reaction as an example, the reaction can be divided into two half reactions of cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), wherein the OER process involves a four-electron transfer process, is slow in kinetics, and generally has a high overpotential, thus greatly limiting the efficiency of water splitting. In addition, the existing electrocatalysis system is basically a water system, so that an efficient and stable OER catalyst is developed, the method is beneficial to the carrying out of catalytic decomposition reaction of various water systems, and the efficient storage and clean conversion of energy are realized.
Among many water electrolysis technologies, proton exchange membrane systems (PEM) are widely used in electrocatalytic reactions due to their advantages of high mass transfer efficiency, high product purity, low pollution, etc., and are one of the currently available large-scale water electrolysis technologies, but proton exchange membranes are limited to use in acidic media. In addition, since the catalyst material in an acidic medium is corroded, resulting in a significant decrease in the stability and activity thereof, the research and technical development of the existing OER mainly focuses on the research of the catalyst in a basic medium. Therefore, the development of an efficient OER catalyst which stably works in an acid environment has great significance for the field of hydrogen production by PEM water electrolysis.
The current research shows that the acidic OER catalyst can stably catalyze and decompose waterOf (2) is only iridium dioxide (IrO)2) And derivatives thereof. However, IrO2The use of the system for acidic OER still presents significant drawbacks: the stability is strong, but the activity is relatively poor; meanwhile, iridium is a noble metal, which is expensive and not suitable for large-scale development. Therefore, for the development of iridium-based OER catalysts, it is of great significance to improve the catalyst activity and reduce the amount of iridium used, even to find a low-priced substitute for iridium.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an iridium-tungsten alloy nanomaterial, a preparation method thereof, and an application thereof as an acidic oxygen evolution reaction electrocatalyst, wherein the usage amount of noble metal iridium is reduced, and higher OER activity and stability are obtained.
In order to achieve the purpose, the technical scheme is as follows:
1. the invention provides a preparation method of an iridium-tungsten alloy nano material, which comprises the following steps:
and (2) mixing the tungsten source solution with weak acid, an iridium source and ammonium salt uniformly in sequence, adding a carrier, preparing an oxide nanowire intermediate through a high-temperature high-pressure hydrothermal reaction, and reducing the obtained oxide nanowire intermediate at a high temperature in a reducing atmosphere to obtain the iridium-tungsten alloy nano material.
Preferably, the tungsten source compound in the tungsten source solution is selected from one or more of alkali metal salt, alkaline earth metal salt or ammonium salt of tungstate radical; wherein the concentration of the tungstate radical in the tungsten source solution is 0.01-0.03 mol/L, and more preferably 0.012-0.013 mol/L.
Preferably, the tungsten source compound is selected from one or more of sodium tungstate, calcium tungstate and ammonium tungstate.
In the invention, the pH value of the tungsten source solution is preferably adjusted to 1-4, and more preferably 2.5-3.2.
Preferably, the weak acid is selected from one or more of acetic acid, oxalic acid and hypophosphorous acid. The concentration of the weak acid in the tungsten source solution is preferably 0.03-0.1 mol/L, and more preferably 0.035-0.045 mol/L; more preferably 0.035 to 0.04 mol/L.
Preferably, the iridium source is selected from one or more of chloroiridate, ammonium chloroiridate and sodium chloroiridate.
Preferably, the ammonium salt is one or more selected from ammonium sulfate, ammonium chloride and ammonium nitrate.
Wherein the concentration of ammonium radicals in the ammonium salt in the tungsten source solution is preferably 0.15-0.17 mol/L.
In the invention, the molar ratio of the iridium source to the tungsten source in the solution is preferably 1: 8.5-1: 19.
Preferably, the carrier is selected from one or more of carbon cloth, carbon paper and conductive glass; wherein, the carbon cloth and the carbon paper are preferably subjected to hydrophilic treatment before use.
The hydrophilic treatment preferably comprises soaking in concentrated sulfuric acid and concentrated nitric acid, and the like.
Preferably, the temperature of the hydrothermal reaction is 120-190 ℃; the time of the hydrothermal reaction is 10-20 h.
Preferably, the high-temperature reduction temperature is 500-900 ℃; the high-temperature reduction time is 12-48 h.
In the present invention, preferably, the reducing atmosphere is argon-hydrogen mixed gas or carbon monoxide mixed gas; among them, the hydrogen content is preferably 3% to 20%.
2. The invention provides an iridium-tungsten alloy nano material prepared by the preparation method, wherein the mass content of iridium is 3-10%.
The mass of the iridium is more preferably 7-10%; specifically, the content is 3%, 4%, 4.5%, 5%, 7%, 7.5%, 8%, 9%, 10%, or a range in which any of the above values is an upper limit value or a lower limit value.
3. The invention provides an iridium-tungsten alloy nano material prepared by the preparation method or an application of the iridium-tungsten alloy nano material as an acidic oxygen evolution reaction electrocatalyst.
Specifically, the invention provides an acidic oxygen evolution reaction working electrode, which is obtained by loading the iridium-tungsten alloy nano material on the surface of a carrier material.
Compared with the prior art, the iridium-doped tungsten oxide is directly loaded on the carbon cloth through hydrothermal reaction, and the iridium-tungsten alloy nano material is obtained through high-temperature reduction. The obtained nano material is loaded on carbon cloth and can be directly used as an electrode of an electrolytic cell, so that the problems of low diffusion rate, poor conductivity and the like caused by the use of a binder are avoided, and the electrode manufacturing process is simplified. Compared with the traditional IrO2The catalyst takes noble metal Ir as a main structure, the defects of high price and low reserve volume greatly limit the large-scale development of the catalyst, and the invention selects metal tungsten with rich content, low price and acid corrosion resistance as the main structure, thereby greatly reducing the dosage of the iridium and reducing the cost. Meanwhile, the reduction of active sites improves the atom utilization rate of iridium, and accords with the green chemical concept. And commercial IrO2Compared with the prior art, the alloy material has higher OER activity and stability and has higher industrial application prospect.
In addition, the acidic OER related to the present invention has a fatal defect that the non-noble metal catalyst is easily subjected to surface reconstruction and thus is deactivated in an acidic solution, and the currently known materials for stably catalyzing the acidic OER are limited to noble metal iridium-based catalysts. The material takes non-noble metal tungsten as a main material, so that the catalytic performance is greatly improved, and the material has excellent stability. Constant current (10 mA/cm) for 20 continuous hours2) After the test, the overpotential of the alloy is increased by only 20 mV.
Drawings
FIG. 1 is an XRD spectrum of IrW nano-alloy material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of IrW nm alloy material prepared in example 1 of the present invention;
FIG. 3 is a comparative LSV curve of IrW nm alloy material prepared in example 1 of the present invention before and after 20h test;
FIG. 4 shows Ir nanoalloy material and commercial IrO prepared in example 1 of the present invention2The timing potential analysis comparison graph of (1);
FIG. 5 is a comparative LSV curve of IrW nm alloy materials prepared in examples 1-4 of the present invention.
Detailed Description
In order to further illustrate the present invention, the iridium tungsten alloy nanomaterial provided by the present invention, the preparation method thereof, and the application thereof as an acidic oxygen evolution reaction electrocatalyst are described in detail below with reference to examples.
Example 1
IrW preparation of alloy nano material:
weighing 4.123g of sodium tungstate dihydrate and 4.41g of oxalic acid, stirring and dissolving in 100ml of water, dropwise adding 1mol/L dilute sulfuric acid, detecting by using an acidic precise pH test paper, and adjusting the pH to 3.2 to serve as mother liquor for later use. Taking 20ml of mother liquor, weighing 1.586g of ammonium sulfate in the mother liquor, stirring for dissolving, weighing 0.25g of chloroiridic acid (with the effective content of 35%) in a beaker containing the solution after the solution is clarified, and quickly stirring until the chloroiridic acid is completely dissolved, wherein the solution is brown and transparent. The brown solution is transferred into a 25ml polytetrafluoroethylene hydrothermal reaction kettle, and a piece of hydrophilic carbon cloth (2 cm multiplied by 2cm and soaked by concentrated sulfuric acid and concentrated nitric acid for one week in advance) is placed in the reaction kettle and is leaned against the wall of the container to be kept vertical. Putting the precursor into a stainless steel reaction kettle shell, screwing a kettle cover, and reacting in an oven at 180 ℃ for 18h to obtain the iridium-doped tungsten trioxide nanowire precursor growing on the carbon cloth. And (3) oscillating and cleaning the carbon cloth, drying the carbon cloth in vacuum at 60 ℃, and finally reducing the carbon cloth in a tubular furnace in 3% argon-hydrogen mixed gas at 600 ℃ for 12 hours to obtain IrW alloy nanoparticles.
The IrW alloy nano-material prepared by the method is shown by an inductively coupled atomic absorption spectrometry (ICP-AES) test that: the iridium content was 7 wt%.
The crystal structure of the IrW alloy nano-material prepared in the above way is the same as that of W metal, and the X-ray diffraction spectrum (XRD) thereof is shown in figure 1.
The prepared IrW alloy nano material can be determined to be in a nano particle shape through a scanning electron microscope picture, and the scanning electron microscope picture is shown as 2.
The method for testing the acidic OER performance of the prepared IrW alloy nano material comprises the following steps:
data collection was performed using a chi660e electrochemical workstation. The test is carried out by adopting a three-electrode electrolytic cell, and the working electrode is the load prepared by the methodIrW carbon cloth made of alloy nano material, reference electrode Ag/AgCl electrode, counter electrode platinum sheet electrode, and electrolyte 0.5mol/L H2SO4And (3) solution.
And (3) activity test: linear Sweep Voltammogram (LSV), test voltage range 0.6-1.6V vs. sce, sweep rate 5 mV/s. And testing for several times until the data is stable, and taking the last time.
And (3) stability testing: chronopotentiometric analysis (CP) with a test current density of 10mA/cm2And testing for 20h, and recording a voltage curve under constant current density for 20h continuously.
For commercial IrO under the same conditions2OER performance testing was performed for comparison.
The experimental results are as follows:
the electrochemical results are shown in fig. 3, fig. 4 and table 1.
LSV results indicate commercial IrO2At 10mA/cm2The overpotential at current density of (a) is 485mV, while the overpotential of the IrW alloy material of this example is only 261mV under the same test conditions.
CP results indicate commercial IrO2Starting to decay until deactivation after 3h of the test, while the IrW alloy material of this example was stable after 20h under the same test conditions, the tested material was subjected to the LSV test and the overpotential was found to rise by only 20mV (10 mA/cm)2)。
In conclusion, the IrW alloy material prepared by the method can be applied to acidic OER catalysts, and the activity and stability of the IrW alloy material far exceed those of current commercial IrO2。
Examples 2 to 4
The remaining conditions were the same as in example 1 except that only the amount of the Ir source added was changed (as shown in Table 1), and the OER catalytic performance is shown in Table 1.
The comparison of the different examples shows that the catalyst activity is optimized when the Ir content is 7 wt%, and the catalytic performance does not increase significantly when the Ir content is increased further.
TABLE 1 summary of Ir loadings and electrochemical properties in examples 1-4
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of an iridium-tungsten alloy nano material is characterized by comprising the following steps: the method comprises the following steps:
mixing a tungsten source solution with weak acid, an iridium source and ammonium salt in sequence, adding a carrier, and then preparing an oxide nanowire intermediate through a high-temperature high-pressure hydrothermal reaction, and reducing the obtained oxide nanowire intermediate at a high temperature in a reducing atmosphere to obtain an iridium-tungsten alloy nano material; wherein, the mass content of iridium is 3-10%;
the temperature of the hydrothermal reaction is 120-190 ℃; the time of the hydrothermal reaction is 10-20 h.
2. The preparation method according to claim 1, wherein the tungsten source compound in the tungsten source solution is selected from one or more of alkali metal salts, alkaline earth metal salts or ammonium salts including tungstate radicals;
wherein the concentration of the tungstate radical in the tungsten source solution is 0.01-0.03 mol/L;
wherein the pH value of the tungsten source solution is 1-4.
3. The method of claim 1, wherein: the weak acid is selected from one or more of acetic acid, oxalic acid and hypophosphorous acid;
wherein the concentration of the weak acid in the tungsten source solution is 0.03-0.1 mol/L.
4. The method of claim 1, wherein: the iridium source is selected from one or more of chloroiridate, ammonium chloroiridate and sodium chloroiridate;
wherein the molar ratio of the iridium source to the tungsten source in the solution is 1: 8.5-1: 19.
5. The method of claim 1, wherein: the ammonium salt is selected from one or more of ammonium sulfate, ammonium chloride and ammonium nitrate;
wherein the concentration of ammonium radicals in the ammonium salt in the tungsten source solution is 0.15-0.17 mol/L.
6. The method of claim 1, wherein: the carrier is selected from one or more of carbon cloth, carbon paper and conductive glass;
wherein the carbon cloth and the carbon paper are subjected to hydrophilic treatment before use;
the hydrophilic treatment comprises soaking in concentrated sulfuric acid and concentrated nitric acid.
7. The method of claim 1, wherein: the temperature of the high-temperature reduction is 500-900 ℃; the high-temperature reduction time is 12-48 h;
wherein the reducing atmosphere is argon-hydrogen mixed gas;
the hydrogen content is 3-20%.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053926A (en) * | 2000-05-31 | 2002-02-19 | Honda Motor Co Ltd | Hydrogen storage alloy powder and on-vehicle hydrogen storage tank |
| CN1538482A (en) * | 2003-04-17 | 2004-10-20 | 中国科学院电子学研究所 | Dipped barium tungsten cathode based on tungsten irridium alloy and its preparation method |
| CN103537293A (en) * | 2012-07-12 | 2014-01-29 | 北京大学 | Catalyst used for preparing single-walled carbon nanotube with chirality selectivity and conductivity selectivity as well as preparation method and application thereof |
| CN103972519A (en) * | 2013-02-01 | 2014-08-06 | 福特全球技术公司 | Catalyst assembly including an intermetallic compound of iridium and tungsten |
| CN106824188A (en) * | 2017-01-12 | 2017-06-13 | 东南大学 | A kind of preparation of tungsten-based catalyst of carrying transition metal and application process |
| CN108470917A (en) * | 2018-04-19 | 2018-08-31 | 华南理工大学 | A kind of carbon carries difunctional electrocatalysis material of compound and preparation method thereof between iridium manganese Metal |
| CN108588740A (en) * | 2018-04-12 | 2018-09-28 | 商洛学院 | A kind of preparation method of Au-Ir nano chain elctro-catalysts for water-splitting production oxygen |
| CN108722406A (en) * | 2018-06-04 | 2018-11-02 | 山东麟丰化工科技有限公司 | A kind of tungsten-based catalyst, preparation method and its purposes in isobutane alkylation reaction |
| CN108772569A (en) * | 2018-06-25 | 2018-11-09 | 天津大学 | A kind of hydrothermal preparing process of superfine nano tungsten powder |
| CN111017997A (en) * | 2019-12-24 | 2020-04-17 | 浙江工商大学 | Hollow mesoporous defective tungsten trioxide nanospheres and preparation method and application thereof |
| CN111420658A (en) * | 2020-04-22 | 2020-07-17 | 上海大学 | Ir/Ru alloy oxygen precipitation catalyst, and preparation method and application thereof |
| CN111570788A (en) * | 2020-05-21 | 2020-08-25 | 中国科学院福建物质结构研究所 | Bimetal nano material, catalyst, preparation method and application thereof |
-
2020
- 2020-12-28 CN CN202011583722.6A patent/CN112760677B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053926A (en) * | 2000-05-31 | 2002-02-19 | Honda Motor Co Ltd | Hydrogen storage alloy powder and on-vehicle hydrogen storage tank |
| CN1538482A (en) * | 2003-04-17 | 2004-10-20 | 中国科学院电子学研究所 | Dipped barium tungsten cathode based on tungsten irridium alloy and its preparation method |
| CN103537293A (en) * | 2012-07-12 | 2014-01-29 | 北京大学 | Catalyst used for preparing single-walled carbon nanotube with chirality selectivity and conductivity selectivity as well as preparation method and application thereof |
| CN103972519A (en) * | 2013-02-01 | 2014-08-06 | 福特全球技术公司 | Catalyst assembly including an intermetallic compound of iridium and tungsten |
| CN106824188A (en) * | 2017-01-12 | 2017-06-13 | 东南大学 | A kind of preparation of tungsten-based catalyst of carrying transition metal and application process |
| CN108588740A (en) * | 2018-04-12 | 2018-09-28 | 商洛学院 | A kind of preparation method of Au-Ir nano chain elctro-catalysts for water-splitting production oxygen |
| CN108470917A (en) * | 2018-04-19 | 2018-08-31 | 华南理工大学 | A kind of carbon carries difunctional electrocatalysis material of compound and preparation method thereof between iridium manganese Metal |
| CN108722406A (en) * | 2018-06-04 | 2018-11-02 | 山东麟丰化工科技有限公司 | A kind of tungsten-based catalyst, preparation method and its purposes in isobutane alkylation reaction |
| CN108772569A (en) * | 2018-06-25 | 2018-11-09 | 天津大学 | A kind of hydrothermal preparing process of superfine nano tungsten powder |
| CN111017997A (en) * | 2019-12-24 | 2020-04-17 | 浙江工商大学 | Hollow mesoporous defective tungsten trioxide nanospheres and preparation method and application thereof |
| CN111420658A (en) * | 2020-04-22 | 2020-07-17 | 上海大学 | Ir/Ru alloy oxygen precipitation catalyst, and preparation method and application thereof |
| CN111570788A (en) * | 2020-05-21 | 2020-08-25 | 中国科学院福建物质结构研究所 | Bimetal nano material, catalyst, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| IrW nanobranch as an advanced electrocatalyst for pH-universal overall water splitting;Luhong Fu et al;《NANOSCALE》;20190409;第11卷(第18期);第8898-8905页、Supporting Information * |
| Sudesh Kumari et al.A low-noble-metal W1-xIrxO3-d water oxidation electrocatalyst for acidic media via rapid plasma synthesis.《Energy & Environmental Science》.2017,第2432-2440页. * |
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