CN111375408B - Preparation method and application of iridium oxide nanoparticle catalyst - Google Patents
Preparation method and application of iridium oxide nanoparticle catalyst Download PDFInfo
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- CN111375408B CN111375408B CN202010095220.2A CN202010095220A CN111375408B CN 111375408 B CN111375408 B CN 111375408B CN 202010095220 A CN202010095220 A CN 202010095220A CN 111375408 B CN111375408 B CN 111375408B
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910000457 iridium oxide Inorganic materials 0.000 title claims abstract description 157
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 149
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 110
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 34
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- 239000010409 thin film Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
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- 238000000576 coating method Methods 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
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- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 17
- 229910001887 tin oxide Inorganic materials 0.000 claims description 17
- 239000010408 film Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
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- 229910052719 titanium Inorganic materials 0.000 claims description 11
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- 229910052799 carbon Inorganic materials 0.000 claims description 5
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
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- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention discloses a preparation method and application of an iridium oxide nanoparticle catalyst. The invention solves the problem that the iridium oxide nanoparticles generated by calcining the iridium-containing compound are agglomerated to form large particles by utilizing the film formed by the polymer in the mixed solution, thereby obtaining the iridium oxide nanoparticles with small particle size. In addition, the invention also uses a plasma generator to remove the residual polymer in the calcining process, and increases the contact area of the iridium oxide nano particles, thereby improving the catalytic efficiency of the iridium oxide nano particles.
Description
Technical Field
The invention belongs to the field of hydrogen production and oxygen evolution by electrochemically decomposing water with a noble metal catalyst, and particularly relates to a preparation method and application of an iridium oxide nanoparticle catalyst.
Background
With the rapid consumption of non-renewable energy sources such as coal, oil, natural gas, etc. and the increasing environmental pollution problem, people are urgently required to use renewable clean energy sources such as wind energy, solar energy, etc. to replace fossil fuels. Due to the discontinuity and fluctuation of wind energy, solar energy and the like from natural factors, energy conversion and storage technologies with high efficiency and low cost need to be developed, for example, energy storage devices such as lithium ion batteries or hydrogen production devices by electrolyzing water are adopted. The hydrogen is an ideal green energy carrier in the future due to high calorific value, cleanness and no pollution. The most perfect closed loop for cleanly utilizing hydrogen energy uses hydrogen as a carrier, and hydrogen is produced by electrolyzing water by electric energy generated by renewable clean energy, and a fuel cell uses hydrogen to produce electric energy, so that no pollutant is produced in the whole process. However, the key one-cycle electrocatalytic Oxygen Evolution Reaction (OER) in this loop is a thermodynamically upslope reaction involving a complex four-proton coupled electron transfer process, and the slow kinetic process poses a significant challenge for large-scale use of these renewable energy devices. Therefore, it is important to develop an efficient and durable OER catalyst to lower the reaction barrier and improve the conversion efficiency.
At present, there are three main types of hydrogen production devices by water electrolysis: alkaline electrolyzers, solid oxide electrolyzers and Proton Exchange Membrane (PEM) electrolyzers. The three types of electrolytic cells have the advantages and disadvantages, such as cheap alkaline electrolytic cell devices, mature technologies, low electrolytic efficiency, low working current and difficulty in adapting to large-range current fluctuation; the solid oxide electrolytic cell can effectively utilize heat energy to reduce the working voltage and has high efficiency, but generally works at high temperature, and belongs to an electrolytic device used in special scenes. The PEM electrolytic cell adopts a polymer proton exchange membrane as a diaphragm, has the advantages of large working current range, wide energy input range, compact structure, capability of obtaining high-purity hydrogen and the like, but is generally in a strong acid environment at present, and has higher requirements on materials and higher cost. Generally, PEM electrolyzers are widely recognized as the most promising hydrogen production plants from electrolyzed water in the field of hydrogen energy due to numerous advantages. As mentioned above, PEM electrolyzers are strongly acidic environments, placing higher demands on OER catalysts. Currently, the main metals suitable for use in PEM electrolyser OER catalysts are the oxides of the noble metals iridium. Because of the rare and high price of noble metal iridium, iridium oxide is still the most suitable catalytic material for the OER electrode of the PEM electrolytic cell. Therefore, the development of iridium oxide catalysts with higher OER catalytic efficiency to reduce their actual loading has become an important research context for PEM cell OER catalysts.
Currently, the preparation methods of iridium oxide mainly include thermal oxidation, sputtering, electrochemical oxidation and the like. Such as heating metallic iridium powder to 1000 deg.c in air or oxygen to produce iridium oxide, the iridium oxide obtained by this method has good crystallinity but relatively large particles. The other method is to convert chloroiridic acid into iridium hydroxide precipitate under the action of strong alkalinity, obtain blue iridium hydroxide powder after washing, filtering and drying, and finally dehydrate at a higher temperature to generate black iridium oxide. In addition, sputtering requires relatively expensive equipment and post-treatment such as thermal oxidation, and electrochemical oxidation is difficult to prepare on a large scale, so that the application is limited. Therefore, there is a need to develop a simple, fast, low cost, and easily scalable process for the preparation of iridium oxide electrocatalysts with high OER catalytic activity.
Disclosure of Invention
Based on the above, the invention aims to solve the problems of small specific surface area, low catalytic activity and high preparation cost of iridium oxide, and one of the purposes of the invention is to provide a preparation method of an iridium oxide nanoparticle catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step S1: uniformly coating a mixed solution containing a polymer and an iridium-containing compound on the treated conductive substrate, and drying to obtain a thin film material deposited on the conductive substrate, wherein the thin film material is formed by the polymer and the iridium-containing compound is uniformly dispersed in the thin film material formed by the polymer;
step S2: calcining the film material obtained in the step S1 at 250-600 ℃ to obtain an iridium oxide nanoparticle material which is deposited on the treated conductive substrate and has a small particle size, an amorphous shape and a porous structure;
step S3: the iridium oxide nanoparticle material obtained in step S2 was subjected to plasma generator to remove the polymer remaining on the iridium oxide nanoparticle material.
Preferably, the conductive substrate in step S1 needs to be pretreated before use, and the pretreatment specifically includes: firstly, sequentially placing a conductive substrate in acetone and ethanol for ultrasonic treatment, then cleaning and drying the treated conductive substrate by using deionized water, then placing the dried conductive substrate in a plasma generator cleaning machine and treating in the atmosphere of air, and finally obtaining the treated conductive substrate.
Preferably, the conductive substrate is any one of fluorine-doped tin oxide, indium-doped tin oxide, a metal titanium sheet, carbon cloth and carbon paper.
Preferably, the iridium-containing compound in step S1 is any one of iridium chloride, chloroiridic acid, iridium acetate, and sodium chloroiridate.
Preferably, the polymer in step S1 is any one of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, and block copolymer.
Preferably, the mass fraction of the iridium-containing compound in the mixed solution in the step S1 is 0.5-20%, and the mass fraction of the polymer in the mixed solution in the step S1 is 1-20%.
Preferably, the mixed solution in the step S1 is uniformly coated on the treated conductive substrate by a spin coater.
Preferably, the processing time of the iridium oxide nanoparticle thin film material in the step S3 in the plasma generator is 5S-60 min.
Further, the invention also aims to provide application of the iridium oxide nanoparticle material catalyst in hydrogen production and oxygen evolution through water electrolysis.
Compared with the prior art, the invention has the following beneficial effects:
(1) the iridium oxide nanoparticle material prepared by the method is an amorphous nanoparticle material with small particle size and ultrahigh electrochemical activity area, shows excellent oxygen precipitation activity in an acid electrolyte, and has ultralow overpotential, Tafel slope and ultrahigh quality activity.
(2) According to the invention, the iridium-containing compound is uniformly attached to the conductive substrate by utilizing the film formed by the polymer on the conductive substrate, and the polymer prevents the iridium-containing compound from agglomerating to form large particles when being calcined to generate the iridium oxide nanoparticles, so that the iridium oxide nanoparticles with small particle size are obtained. In addition, the obtained iridium oxide nanoparticle material is treated by using a plasma generator to remove polymers remained on the iridium oxide nanoparticle material in the calcining process, so that on one hand, the exposed rate of the iridium oxide nanoparticles is improved to increase the contact area of the iridium oxide nanoparticles, and on the other hand, the surfaces of the iridium oxide nanoparticles are rich in hydroxyl groups, thereby improving the catalytic efficiency of the iridium oxide nanoparticles.
(3) The method pretreats the conductive substrate, removes impurities on the surface of the conductive substrate, ensures that the surface of the conductive substrate has hydrophilicity, ensures that the conductive substrate and the mixed solution have better affinity, is favorable for the mixed solution to be coated on the conductive substrate more uniformly, is also favorable for the iridium oxide nano particles to be attached to the conductive substrate, and in addition, the polymer further promotes the attachment and dispersion of the iridium oxide nano particles on the conductive substrate, so that the obtained iridium oxide nano particles are not easy to fall off from the surface of the conductive substrate, thereby showing excellent catalytic activity and long-term oxygen precipitation stability.
(4) The invention adopts cheap, nontoxic and environment-friendly raw materials, thereby not only saving the cost, but also protecting the environment. In addition, the preparation process is simple, complex and expensive equipment is not needed, the iridium oxide nanoparticle material loaded on a large-area conductive substrate can be prepared, the iridium oxide nanoparticle powder material with high dispersibility can also be prepared, the batch generation is easy, the industrial production prospect is realized, and the advantages are realized in the later-stage technological achievement conversion process.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
FIG. 2 is Scanning Electron Microscope (SEM) spectra of iridium oxide nanoparticles calcined at different temperatures, wherein a is SEM spectrum of iridium oxide nanoparticles calcined at 300 ℃ and b is SEM spectrum of iridium oxide nanoparticles calcined at 400 ℃; c is SEM spectrum of iridium oxide nano particle prepared by calcining at 500 ℃; d is SEM spectrum of iridium oxide nano particle prepared by calcining at 600 ℃.
FIG. 3 is an XRD pattern of iridium oxide nanoparticles loaded on fluorine doped tin oxide (FTO) and obtained by calcination at 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, respectively.
Fig. 4 is an XRD pattern of iridium oxide nanoparticles obtained by calcination at 300 ℃ and supported on fluorine-doped tin oxide (FTO) before and after plasma generator treatment.
FIG. 5 shows iridium oxide nanoparticles loaded on fluorine-doped tin oxide (FTO) and obtained by calcination at 300 deg.C, 400 deg.C, 500 deg.C, and 600 deg.C respectively in acidic electrolyte environment (0.5mol/L H)2SO4) The polarization curve map of electrochemical oxygen evolution.
FIG. 6 shows the iridium oxide nanoparticles loaded on fluorine-doped tin oxide (FTO) and obtained by calcination at 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C respectively in acidic electrolyte environment (0.5mol/L H)2SO4) Tafel curve map of (1).
FIG. 7 shows the iridium oxide nanoparticles loaded on fluorine-doped tin oxide (FTO) and obtained by calcination at 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C respectively in acidic electrolyte environment (0.5mol/L H)2SO4) Impedance curve plot at 1.55V versus standard hydrogen electrode potential.
FIG. 8 shows iridium oxide nanoparticles loaded on fluorine-doped tin oxide (FTO) and obtained by calcination at 300 deg.C, 400 deg.C, 500 deg.C, and 600 deg.C respectively in acidic electrolyte environment (0.5mol/L H)2SO4) Lower dual capacitor active area.
FIG. 9 shows iridium oxide nanoparticles calcined at 300 ℃ and supported on fluorine doped tin oxide (FTO) in an acidic electrolyte environment (0.5mol/L H) before and after treatment with a plasma generator2SO4) The polarization curve map of electrochemical oxygen evolution.
FIG. 10 shows iridium oxide nanoparticles calcined at 300 ℃ and supported on fluorine-doped tin oxide (FTO) in an acidic electrolyte environment (0.5mol/L H) before and after treatment with a plasma generator2SO4) Tafel yeast (Tafel)A line map.
FIG. 11 shows iridium oxide nanoparticles calcined at 300 ℃ and supported on fluorine doped tin oxide (FTO) in an acidic electrolyte environment (0.5mol/L H) before and after treatment with a plasma generator2SO4) Impedance curve plot at 1.55V versus standard hydrogen electrode potential.
FIG. 12 shows iridium oxide nanoparticles calcined at 300 ℃ and supported on fluorine doped tin oxide (FTO) in an acidic electrolyte environment (0.5mol/L H) before and after treatment with a plasma generator2SO4) Lower dual capacitance active area spectrum.
FIG. 13 shows iridium oxide nanoparticles calcined at 300 ℃ and supported on fluorine doped tin oxide (FTO) in an acidic electrolyte environment (0.5mol/L H) before and after treatment with a plasma generator2SO4) The double-capacitance active area spectrum of the following formula, and iridium oxide nano particle plasma generator treatment on fluorine-doped tin oxide (FTO), wherein the iridium oxide nano particle plasma generator treatment is obtained by calcining at 400 ℃, 500 ℃ and 600 ℃ respectively and is loaded on fluorine-doped tin oxide (FTO) in an acid electrolyte environment (0.5mol/L H)2SO4) Mass activity profile at 1.55V voltage.
Detailed Description
The technical solution of the present invention is further clearly and completely described below with reference to examples, wherein the raw materials used in the examples of the present invention are all commercially available.
Example 1
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 0.5%, the mass fraction of the polyvinylpyrrolidone is 1%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, wherein the spin coater uniformly coats glue at 500r/min for 10 seconds and then continues for 1800 seconds at 2000r/min during coating, and a thin film material deposited on the FTO conductive substrate is obtained after drying, and is formed by polyvinylpyrrolidone and uniformly dispersed in the thin film material formed by polyvinylpyrrolidone.
And 3, step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 250 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3 hours to obtain the iridium oxide nanoparticle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 5s to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
Finally, the iridium oxide nanoparticle catalyst prepared by the embodiment is applied to hydrogen production and oxygen evolution by water electrolysis.
Example 2
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
And 2, step: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 20%, the mass fraction of the polyvinylpyrrolidone is 20%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, wherein the spin coater uniformly coats glue at 500r/min for 10 seconds and then continues at 2000r/min for 1800 seconds during coating, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3h to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 60min to remove the polymer remained on the iridium oxide nanoparticle material, so that the iridium oxide nanoparticles are completely exposed.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 3
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, wherein the spin coater uniformly coats glue at 500r/min for 10 seconds and then continues at 2000r/min for 1800 seconds during coating, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 300 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3h to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 4
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate for 5-15 min by using ultrasonic waves, cleaning the FTO conductive substrate after ultrasonic treatment by using deionized water, drying, and finally treating the dried FTO conductive substrate for 15min in an air atmosphere by using a plasma generator cleaning machine to obtain the treated FTO conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, uniformly coating the FTO conductive substrate for 10 seconds at 500r/min by the spin coater during coating, then continuing for 1800 seconds at 2000r/min, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3h to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 5
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, wherein the spin coater uniformly coats glue at 500r/min for 10 seconds and then continues at 2000r/min for 1800 seconds during coating, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 500 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3h to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 6
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on the treated FTO conductive substrate through a spin coater, wherein the spin coater uniformly coats glue at 500r/min for 10 seconds and then continues at 2000r/min for 1800 seconds during coating, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3h to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 7
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the titanium sheet conductive substrate in acetone and ethanol, washing the titanium sheet conductive substrate with ultrasonic waves for 5-15 min for treatment, then washing the titanium sheet conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried titanium sheet conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated titanium sheet conductive substrate.
Step 2: dispersing chloroiridic acid and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the chloroiridic acid in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on a treated titanium sheet conductive substrate through a spin coater, uniformly coating the titanium sheet conductive substrate by the spin coater at 500r/min for 10 seconds during coating, then continuing at 2000r/min for 1800 seconds, and drying to obtain a thin film material deposited on the titanium sheet conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone and the chloroiridic acid is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3 hours to obtain the iridium oxide nano particle material which is loaded on the titanium sheet conductive substrate and has small particle size, amorphous shape and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Example 8
A preparation method of an iridium oxide nanoparticle catalyst specifically comprises the following steps:
step 1: and sequentially placing the FTO conductive substrate in acetone and ethanol, cleaning the FTO conductive substrate with ultrasonic waves for 5-15 min for treatment, cleaning the FTO conductive substrate subjected to ultrasonic treatment with deionized water, drying, and finally treating the dried FTO conductive substrate with a plasma generator cleaning machine in an air atmosphere for 15min to obtain the treated FTO conductive substrate.
Step 2: the preparation method comprises the steps of dispersing iridium acetate and polyvinylpyrrolidone in deionized water to prepare a mixed solution, wherein the mass fraction of the iridium acetate in the mixed solution is 5%, the mass fraction of the polyvinylpyrrolidone is 10%, sucking 50 mu L of the mixed solution, uniformly coating the mixed solution on a treated FTO conductive substrate through a spin coater, homogenizing for 10 seconds at 500r/min by the spin coater during coating, then continuing for 1800 seconds at 2000r/min, and drying to obtain a thin film material deposited on the FTO conductive substrate, wherein the thin film material is formed by polyvinylpyrrolidone, and the iridium acetate is uniformly dispersed in the thin film material formed by the polyvinylpyrrolidone.
And step 3: and (3) putting the film material obtained in the step (2) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min, calcining, and keeping at the temperature for 3 hours to obtain the iridium oxide nano particle material which is loaded on the FTO conductive substrate and has a small particle size, an amorphous structure and a porous structure.
And 4, step 4: and (3) placing the iridium oxide nanoparticle material obtained in the step (3) in a plasma generator, and treating the iridium oxide nanoparticle material by using the plasma generator in an air atmosphere for 10min to remove the polymer remained on the iridium oxide nanoparticle material so as to completely expose the iridium oxide nanoparticles.
And finally, applying the iridium oxide nanoparticle catalyst prepared by the embodiment to hydrogen and oxygen evolution by water electrolysis.
Comparative example 1
The iridium oxide nanoparticle material was prepared as in example 3, except that the iridium oxide nanoparticle material was not treated in a plasma generator.
Comparative example 2
The iridium oxide nanoparticle material was prepared as in example 4, except that the iridium oxide nanoparticle material was not treated in a plasma generator.
Comparative example 3
The iridium oxide nanoparticle material was prepared as in example 5, except that the iridium oxide nanoparticle material was not treated in a plasma generator.
Comparative example 4
The iridium oxide nanoparticle material was prepared as in example 6, except that the iridium oxide nanoparticle material was not treated in a plasma generator.
Fig. 2 is SEM spectra of the iridium oxide nanoparticle materials obtained in examples 3, 4, 5, and 6, and it can be seen that nanoparticle structures with small particle sizes were obtained at different calcination temperatures of 300 to 600 ℃.
Fig. 3 is an XRD spectrum of the iridium oxide nanoparticle materials prepared in examples 3, 4, 5 and 6, and it can be seen from fig. 3 that the crystallinity of the prepared iridium oxide nanoparticle materials decreases as the calcination temperature decreases.
Fig. 4 is an XRD spectrum of the iridium oxide nanoparticle materials prepared in example 3 and comparative example 1, from which it can be seen that the amorphous state of the iridium oxide nanoparticles was not changed by the plasma generator treatment, indicating that the plasma generator treatment has substantially no effect on the crystalline phase of the iridium oxide nanoparticles.
FIGS. 5 and 6 show the iridium oxide nanoparticle materials obtained in examples 3, 4, 5 and 6 in an acid electrolyte (0.5mol/L H)2SO4) The medium polarization curve and the afel slope test, in combination with fig. 5 and 6, can see that from 300 ℃ to 600 ℃, the catalytic performance of the iridium oxide nanoparticles gradually decreases with the increase of the processing temperature.
Fig. 7 shows that the iridium oxide nanoparticle materials prepared in examples 3, 4, 5 and 6 are subjected to impedance testing, and it can be seen from the impedance testing that the electrochemical oxygen evolution kinetics performance is gradually improved as the sample treatment temperature is reduced.
Fig. 8 is a diagram of the electrochemical active area of the catalyst of the iridium oxide nanoparticle materials obtained in examples 3, 4, 5 and 6, and it can be seen from the diagram that the electrochemical active area of the iridium oxide nanoparticles is significantly increased with the decrease of the calcination temperature, which illustrates that the specific surface area of the iridium oxide nanoparticle material is gradually decreased with the increase of the calcination temperature, because the crystallinity of the iridium oxide nanoparticles is increased and some aggregation occurs at high temperature.
FIG. 9 and FIG. 10 are the polarization curve map and Tafel slope map of the iridium oxide nanoparticles obtained in example 3 and comparative example 1, respectively, and it can be seen from FIG. 9 that the catalytic activity of the iridium oxide nanoparticles is significantly improved by the plasma generator treatment at 10mAcm-2The overpotential at the current density is 290mV, which is much lower than 342mV before the treatment, and it can be seen from fig. 10 that the Tafel slope of the iridium oxide nanoparticles before and after the plasma generator treatment does not change significantly.
Fig. 11 is a graph of a resistance curve of the iridium oxide nanoparticle materials obtained in example 3 and comparative example 1, and it can be seen from the graph that the electrochemical oxygen evolution kinetic performance of the iridium oxide nanoparticle materials treated by the plasma generator is significantly improved.
Fig. 12 is a diagram of the electrochemical active area of the iridium oxide nanoparticle materials obtained in example 3 and comparative example 1, and it can be seen from the diagram that the electrochemical active area of the iridium oxide nanoparticles treated by the plasma generator is increased, and thus the catalytic performance of the iridium oxide nanoparticles is improved, because the polymer which is not completely removed in the calcination process is removed in the treatment process of the plasma generator, so that rich hydroxyl groups with higher activity are formed on the surface of the iridium oxide, and thus more active sites are exposed, and the catalytic activity of the iridium oxide nanoparticles is improved.
FIG. 13 shows that the iridium oxide nanoparticle materials obtained in example 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 are 1.55The mass activity spectrum under the potential of V is shown in the figure, the mass activity of the obtained iridium oxide nanoparticle catalyst is gradually improved along with the reduction of the calcining temperature, and after the treatment of the plasma generator, the mass activity is twice of that of the untreated iridium oxide nanoparticle catalyst, and the mass activity reaches nearly 1000Ag-1Is very high.
In conclusion, the invention solves the problems of low specific surface area of iridium oxide, low catalytic activity and high preparation cost in the prior art.
The foregoing is only a partial embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The preparation method of the iridium oxide nanoparticle catalyst is characterized by comprising the following steps:
step S1: uniformly coating a mixed solution containing a polymer and an iridium-containing compound on the treated conductive substrate, and drying to obtain a thin film material deposited on the conductive substrate, wherein the thin film material is formed by the polymer and the iridium-containing compound is uniformly dispersed in the thin film material formed by the polymer; wherein the mass fraction of the iridium-containing compound in the mixed solution is 0.5-20%, and the mass fraction of the polymer in the mixed solution in the step S1 is 1-20%;
step S2: calcining the film material obtained in the step S1 at 250-600 ℃ to obtain an iridium oxide nanoparticle material which is deposited on the treated conductive substrate and has a small particle size, an amorphous shape and a porous structure;
step S3: removing the polymer remaining on the iridium oxide nanoparticle material obtained in step S2 with a plasma generator;
the conductive substrate in step S1 needs to be pretreated before use, and the pretreatment specifically includes: firstly, sequentially placing a conductive substrate in acetone and ethanol for ultrasonic treatment, then cleaning and drying the treated conductive substrate by using deionized water, then placing the dried conductive substrate in a plasma generator cleaning machine and treating in the atmosphere of air, and finally obtaining the treated conductive substrate.
2. The method for preparing the iridium oxide nanoparticle catalyst according to claim 1, wherein the conductive substrate is any one of fluorine-doped tin oxide, indium-doped tin oxide, metallic titanium sheet, carbon cloth, and carbon paper.
3. The method of claim 1, wherein the iridium-containing compound in step S1 is any one of iridium chloride, chloroiridic acid, iridium acetate, and sodium chloroiridate.
4. The method for preparing the iridium oxide nanoparticle catalyst according to claim 1, wherein the polymer in the step S1 is any one of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, and block copolymer.
5. The method for preparing the iridium oxide nanoparticle catalyst according to claim 1, wherein the mixed solution in the step S1 is uniformly coated on the treated conductive substrate by a spin coater.
6. The method for preparing the iridium oxide nanoparticle catalyst according to claim 1, wherein the processing time of the iridium oxide nanoparticle film material in the step S3 in the plasma generator is 5S-60 min.
7. An application of the iridium oxide nanoparticle material catalyst is characterized in that the iridium oxide nanoparticle material prepared by the preparation method of the iridium oxide nanoparticle material catalyst according to any one of claims 1 to 6 is applied to hydrogen production and oxygen evolution through water electrolysis.
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| CN113289622B (en) * | 2021-06-25 | 2023-10-24 | 江苏科技大学 | Water-splitting hydrogen production composite material and preparation method thereof |
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