CN115716657B - IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application - Google Patents
IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application Download PDFInfo
- Publication number
- CN115716657B CN115716657B CN202211493924.0A CN202211493924A CN115716657B CN 115716657 B CN115716657 B CN 115716657B CN 202211493924 A CN202211493924 A CN 202211493924A CN 115716657 B CN115716657 B CN 115716657B
- Authority
- CN
- China
- Prior art keywords
- sheet
- nano
- irw
- electrocatalyst
- carbon paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002135 nanosheet Substances 0.000 title claims abstract description 66
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 9
- 239000002121 nanofiber Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 33
- 229910000510 noble metal Inorganic materials 0.000 abstract description 20
- 230000000694 effects Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses IrW oxide nano-sheet electrocatalyst, and a rapid temperature rise and fall preparation method and application thereof in combination with electrodeposition, and belongs to the technical field of catalyst preparation. The scheme comprises the following steps: firstly, uniformly distributed WO 3 nano sheets are grown on carbon paper nano fibers in situ by a hydrothermal method, and then the carbon paper nano sheets are cooled, washed and dried. Ir was then deposited uniformly on the WO 3 nanoplatelets by acidic cathodic electrodeposition, followed by drying. Finally, the sample deposited with Ir is fixed and then placed in a Joule heat rapid temperature rise and fall furnace, and after the temperature rises to 1580K in 1 second, the temperature is rapidly reduced, and the IrW oxide nano-sheet electrocatalyst is prepared. The IrW oxide nano-sheet prepared by the method has high specific surface area and low Ir noble metal consumption, and meanwhile, the catalyst has better stability, and can stabilize the electrolytic water oxygen evolution reaction for more than 30 hours under the acidic condition.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to IrW oxide nano-sheet electrocatalyst, and a rapid temperature rise and drop preparation method and application thereof by combining electrodeposition.
Background
The acidic electrolyzed water hydrogen production is one of the most potential technical means for preparing hydrogen from renewable energy sources due to the advantages of high efficiency, adjustable current density, low energy consumption, small volume and the like. However, the slow four-electron reaction process in the oxygen evolution reaction is a major limiting factor for acidic electrolyzed water. At present, the acid oxygen evolution catalyst with high activity is mostly an iridium/ruthenium-based noble metal catalyst, and for the noble metal catalyst, how to reduce the dosage of the noble metal on the premise of stabilizing high catalytic performance is still a recognized great challenge. Wherein, the substrate with a certain nano structure is loaded with trace noble metal catalyst, and the mass specific activity of the noble metal is improved, so that the catalyst has very important practical promotion effect on hydrogen production by acidic electrolyzed water.
At present, a hydrothermal method is mostly adopted in the acid anode oxygen OER (Oxygen evolution reaction) noble metal catalyst, which is characterized in that noble metal salt is firstly dissolved in ethanol or water, then the noble metal salt solution is mixed with other non-noble metal solutions, then the noble metal-based acid OER catalyst is obtained through high-temperature annealing treatment, and finally the OER catalyst is loaded on an electrode in a spraying or dripping mode for performance test. However, the noble metal utilization rate in the process of preparing the noble metal-based catalyst is not high, and the mass specific activity of the final catalyst is also generally lower, which also greatly increases the preparation cost of the catalyst. In addition, the catalyst is unstable and easy to fall off from the electrode in the subsequent use process, so that the use of the noble metal-based catalyst on a high-quality integrated device is seriously affected.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide IrW oxide nano-sheet electrocatalyst, and a rapid temperature rise and fall-off preparation method and application thereof, which can effectively solve the technical problems of low noble metal mass specific activity, easy electrode falling and poor stability existing in the existing preparation method.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
The invention discloses a method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature rise and drop, which comprises the following steps:
1) In-situ growing uniformly distributed WO 3 nano sheets on the carbon paper nano fibers by a one-step hydrothermal method;
2) Uniformly depositing Ir on the WO 3 nano-sheet by an acidic cathode deposition method;
3) After the WO 3 nano-sheet deposited with Ir is fixed, the temperature is firstly increased to 1580K within 1 second, and then the temperature is rapidly reduced to room temperature at the cooling rate of 1000-1500K/s, so as to prepare the IrW oxide nano-sheet electrocatalyst.
Preferably, in the step 1), the WO 3 nano-sheets uniformly distributed on the carbon paper nano-fibers are grown in situ by a one-step hydrothermal method, and the specific operation is as follows:
step 1: mixing H 2WO4 powder with hydrogen peroxide solution, heating and stirring for reaction until a uniform transparent solution is obtained, and cooling for later use;
Step 2: and carrying out hydrothermal preparation on the uniform transparent solution, hydrochloric acid and acid-treated carbon paper to obtain the WO 3 nano-sheet grown on the carbon paper in situ.
Further preferably, in the step 1, the dosage ratio of the H 2WO4 powder to the hydrogen peroxide solution is (1-1.5) g:40mL, heating temperature is 80-100 ℃, and stirring reaction time is 2-4 h; the mass concentration of the hydrogen peroxide solution is 10-15%.
Further preferably, step 2, the specific operation is as follows:
Adding anhydrous sodium sulfate, concentrated hydrochloric acid and a piece of carbon paper into the uniform transparent solution, reacting for 12 hours at 180-200 ℃, naturally cooling to room temperature, taking out the carbon paper, cleaning and drying to obtain the WO 3 nano-sheet growing on the carbon paper in situ.
Still more preferably, the dosage ratio of the uniform transparent solution, anhydrous sodium sulfate and concentrated hydrochloric acid is 40mL: (0.3-0.5) g:250 μl; the carbon paper used was 2cm by 3mm in size.
Preferably, in the step 2), the WO 3 nano-sheets grown on the carbon paper in situ are used as a substrate, dried and placed in electrolyte, and are used as a cathode in a three-electrode system to carry out electrochemical deposition of Ir atoms;
Wherein, a carbon rod is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a mixed solution of 2mM IrCl 4 and 0.5M H 2SO4 is used as an electrolyte, and the deposition voltage is-1.175V for 30min.
Further preferably, in the step 3), the WO 3 nano sheet deposited with Ir is fixed between two carbon cloths, and is placed in a joule heating rapid heating and cooling furnace to perform rapid heating and cooling treatment.
Preferably, the voltage parameter of the joule heating rapid temperature rise and drop furnace is set to be 30V, the current setting parameter is 80A, the reaching temperature is 1580K, the heating time is 0.25s, and the cooling time is 0.75s.
The invention also discloses IrW oxide nano-sheet electrocatalyst prepared by the method, and the IrW oxide nano-sheet electrocatalyst is used for stabilizing electrolytic water oxygen evolution reaction for more than 30 hours under an acidic condition.
The invention also discloses application of the IrW oxide nano-sheet electrocatalyst in an electrocatalytic decomposition water oxygen evolution reaction.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature rise and drop, firstly, WO 3 nano-sheets uniformly distributed on carbon nano-fibers are grown in situ by a one-step hydrothermal method and serve as substrates for depositing Ir atoms in the next step, and the WO 3 nano-sheets prepared by the process are uniform in transverse dimension (about 2 mu m) and have good binding force with the carbon fibers, so that sufficient deposition sites are provided for subsequent Ir atoms; then Ir is uniformly deposited on the WO 3 nano-sheet by an acidic cathode deposition method, the process can effectively avoid the aggregation phenomenon of Ir atoms, a small amount of active sites of the Ir atoms are exposed on the surface of the nano-sheet as much as possible, and the mass specific activity of Ir noble metals is improved; finally, the IrW oxide nano-sheet electrocatalyst is prepared by rapid temperature rise treatment, the original lattice of WO 3 is broken through by rapid temperature rise in the process, ir atoms loaded on the WO 3 nano-sheet are introduced, the Ir atoms are anchored in the lattice of WO 3 in the rapid temperature drop process, a IrW compound is formed, the electronic structure of the outer layer of the Ir atoms is effectively improved, the adsorption energy of the Ir atoms on an oxygen-containing intermediate in the OER process is optimized, the intrinsic activity of the catalyst is improved, and in addition, the good acting force between WO 3 and carbon nano-fibers and the formation of the IrW compound also greatly improve the stability of the catalyst. Therefore, the method can effectively solve the technical problems of low noble metal mass specific activity, easy falling of the electrode and poor stability in the prior art.
The IrW oxide nano-sheet prepared by the method has high specific surface area and low Ir noble metal consumption, and meanwhile, the catalyst has better stability, and can stabilize the electrolytic water oxygen evolution reaction for more than 30 hours under the acidic condition, so that the catalyst can be applied to the electrocatalytic decomposition water oxygen evolution reaction.
Drawings
FIG. 1 is a flow chart of the preparation of IrW oxide nanoplatelets catalyst used in the present invention;
FIG. 2 is an optical physical image of in situ grown WO 3 and IrW oxide nanoplatelets catalysts obtained according to the present invention;
FIG. 3 is a scanning electron microscope image of the WO 3 oxide nanoplate catalyst of the present invention;
FIG. 4 is a scanning electron microscope image of the WO 3 oxide nanoplate catalyst of the present invention;
FIG. 5 is a scanning electron microscope image of IrW oxide nanoplate catalyst obtained in accordance with the present invention;
FIG. 6 is a distribution image of Ir elements in EDS corresponding to a scanning electron microscope image of IrW oxide nanosheet catalyst obtained according to the present invention;
FIG. 7 is an XRD pattern of IrW oxide nanoplatelets catalyst obtained in accordance with the present invention;
FIG. 8 is a graph showing the OER polarization curve for the IrW oxide nanoplatelets catalyst of the present invention versus linear sweep voltammetry.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 1, the electrodeposition combined rapid temperature rise and fall preparation method of IrW oxide nano-sheet electrocatalyst disclosed by the invention comprises the following steps:
1) In-situ growing WO 3 nano-sheets on the carbon fiber by a one-step hydrothermal method, and taking the nano-sheets as a substrate for depositing Ir atoms in the next step for later use;
Wherein, the specific preparation process comprises the following steps: mixing H 2WO4 powder with hydrogen peroxide solution, heating, stirring, reacting until a uniform transparent solution is obtained, and cooling for later use; the uniform transparent solution is prepared by hydrothermal together with hydrochloric acid and acid-treated carbon paper, and WO 3 nano-sheets grown on the carbon paper in situ are obtained;
preferably, the dosage ratio of the H 2WO4 powder to the hydrogen peroxide solution is (1-1.5) g:40mL, heating temperature is 80-100 ℃, and stirring reaction time is 2-4 h; the mass concentration of the hydrogen peroxide solution is 10% -15%;
Preferably, anhydrous sodium sulfate, concentrated hydrochloric acid and a piece of carbon paper are added into the uniform transparent solution to react for 12 hours at 180-200 ℃, the carbon paper is naturally cooled to room temperature, and the carbon paper is taken out, washed and dried to obtain WO 3 nano-sheets grown on the carbon paper in situ;
further preferably, the dosage ratio of the uniform transparent solution, anhydrous sodium sulfate and concentrated hydrochloric acid is 40mL:
(0.3-0.5) g:250mL; the size of the carbon paper used is 2cm multiplied by 3mm;
2) Taking the WO 3 nano-sheets grown in situ on the carbon fiber obtained in the step 1) as a substrate, drying, placing the substrate in a prepared electrolyte, and taking the substrate as a cathode in a three-electrode system to perform electrochemical deposition of Ir atoms;
in the electrodeposition step, a carbon rod is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the electrolyte is 0.5M H 2SO4+2mM IrCl4, the voltage is-1.175V, and the time is 30min.
3) Fixing the WO 3 nano-sheet deposited with Ir, heating to 1580K in 1 second, and rapidly cooling to obtain IrW oxide nano-sheet electrocatalyst;
Wherein, the specific preparation process comprises the following steps: fixing the WO 3 nano sheet deposited with Ir between two carbon cloths, and placing the carbon cloths in a Joule heating rapid temperature rise and drop furnace (shown in figure 3) for rapid temperature rise and drop treatment;
Specifically, in the process of the Joule heat ultrafast synthesis, the voltage is applied at 30V, the current is 80A, the set temperature is 1580K, the heating time is about 0.25s, and the cooling time is about 0.75s.
Example 1
1) H 2WO4 powder and hydrogen peroxide solution are placed in a flask, uniform and stable solution is formed by heating and stirring, then the solution, a small amount of hydrochloric acid, anhydrous sodium sulfate and carbon paper are placed in a hydrothermal kettle together, and the WO 3 nano-sheet growing on carbon fiber in situ is prepared by a hydrothermal method.
Specifically, 1.25g H 2WO4 powder, 40mL of 12wt% hydrogen peroxide, was placed in a 100mL round bottom flask, stirred at 90℃for 3h, and then cooled to room temperature. Pouring the mixture into a 100mL hydrothermal kettle, adding 0.4g anhydrous sodium sulfate and 250mL concentrated hydrochloric acid, reacting a piece of carbon paper with the thickness of 2cm multiplied by 3mm at 180 ℃ for 12 hours, turning off the furnace and naturally cooling the furnace to room temperature, taking out the carbon paper, washing the carbon paper with deionized water, and drying the carbon paper to obtain the WO 3 nano-sheet growing on the carbon paper in situ. Referring to FIG. 4, the scanning electron microscope photograph shows that the WO 3 nanometer sheet with the transverse dimension of about 2 μm grows on the carbon paper fiber in situ, and the distribution is relatively uniform, so that a plurality of sites are provided for the subsequent deposition of Ir atoms, the utilization rate of the Ir atoms can be improved, and the mass specific activity of noble metal Ir can be improved.
2) Taking the WO 3 nano sheet in-situ grown on the carbon paper obtained in the step 1) as a substrate, cutting the substrate, clamping the substrate on a platinum electrode clamp to serve as a working electrode, taking a carbon rod as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, taking electrolyte as 0.5-M H 2SO4+2mM IrCl4, taking the voltage as-1.175V for 30min, taking out the carbon paper, and drying at 60 ℃ for 2h.
3) And sandwiching the carbon paper on which Ir atoms are deposited between two pieces of carbon cloth with the length of 1cm multiplied by 2cm, placing the carbon paper in a Joule heating rapid temperature rise and reduction furnace, setting the voltage to be 30V, the current to be 80A and the temperature to be 1580K together with a circuit, then carrying out electrifying and heating, and taking out a target sample after the target sample is completely cooled.
As shown in fig. 2, a physical image of the prepared in-situ grown WO 3 and IrW oxide nanoplatelets catalysts is shown. WO 3 on the left and IrW oxide nanoplatelet electrocatalyst on the right.
Referring to fig. 5 and fig. 6, the scanning electron microscope images of the IrW oxide nano-sheet catalyst and the distribution images of Ir elements in the EDS corresponding to the scanning electron microscope images are respectively obtained, and a small amount of Ir elements can be uniformly distributed on the WO 3 nano-sheet, so that aggregation of Ir atoms is avoided, more active sites of limited Ir atoms are exposed on the surface, the utilization rate of Ir atoms is effectively improved, and the mass specific activity of the Ir atoms is improved.
Referring to fig. 7 and 8, the XRD image of the obtained IrW oxide nano-sheet catalyst and the OER polarization curve corresponding to the corresponding linear sweep voltammetry are shown, and it can be seen from the figure that the Ir atoms are well anchored on the WO3 nano-sheet and form IrW compound, so that the electronic structure around the Ir atoms is effectively improved, the oxygen-containing intermediate has proper adsorption energy in the OER process, and the intrinsic OER activity of the catalyst is improved.
Example 2
1) H 2WO4 powder and hydrogen peroxide solution are placed in a flask, uniform and stable solution is formed by heating and stirring, then the solution, a small amount of hydrochloric acid, anhydrous sodium sulfate and carbon paper are placed in a hydrothermal kettle together, and the WO 3 nano-sheet growing on carbon fiber in situ is prepared by a hydrothermal method.
Specifically, 1.5g H 2WO4 powder, 40mL of 15wt% hydrogen peroxide, was placed in a 100mL round bottom flask, stirred at 90℃for 4h, and then cooled to room temperature. Pouring the mixture into a 100mL hydrothermal kettle, adding 0.5g anhydrous sodium sulfate and 250 mu L concentrated hydrochloric acid, reacting a piece of carbon paper with the thickness of 2cm multiplied by 3mm at 180 ℃ for 12 hours, turning off the furnace and naturally cooling the furnace to room temperature, taking out the carbon paper, washing the carbon paper with deionized water, and drying the carbon paper to obtain the WO 3 nano-sheet growing on the carbon paper in situ.
2) Taking the WO 3 nano sheet in-situ grown on the carbon paper obtained in the step 1) as a substrate, cutting the substrate, clamping the substrate on a platinum electrode clamp to serve as a working electrode, taking a carbon rod as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, taking electrolyte as 0.5-M H 2SO4+2mM IrCl4, taking the voltage as-1.175V for 60min, taking out the carbon paper, and drying at 60 ℃ for 2h.
3) And sandwiching the carbon paper on which Ir atoms are deposited between two pieces of carbon cloth with the length of 1cm multiplied by 2cm, placing the carbon paper in a Joule heating rapid temperature rise and reduction furnace, setting the voltage to be 30V, the current to be 80A and the temperature to be 1580K together with a circuit, then carrying out electrifying and heating, and taking out a target sample after the target sample is completely cooled.
In conclusion, the IrW oxide nano-sheet electrocatalyst prepared by the method has high specific surface area and low Ir noble metal dosage, and meanwhile, the catalyst has better stability, and can stabilize the electrolytic water oxygen evolution reaction for more than 30 hours under the acidic condition.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. A method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition and rapid temperature rise and drop, which is characterized by comprising the following steps:
1) In-situ growing uniformly distributed WO 3 nano sheets on the carbon paper nano fibers by a one-step hydrothermal method;
2) Uniformly depositing Ir on the WO 3 nano-sheet by an acidic cathode deposition method;
Taking a WO 3 nano sheet grown on carbon paper in situ as a substrate, drying and then placing the substrate in electrolyte to serve as a cathode in a three-electrode system for electrochemical deposition of Ir atoms;
Wherein, a carbon rod is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a mixed solution of 2mM IrCl 4 and 0.5M H 2SO4 is used as electrolyte, the deposition voltage is-1.175V, and the time is 30min;
3) The WO 3 nano-sheet deposited with Ir is fixed between two carbon cloths and placed in a Joule heating rapid temperature-raising furnace, then the temperature is raised to 1580K in 1 second, and then the temperature is rapidly lowered to room temperature at a cooling rate of 1000-1500K/s, so as to prepare the IrW oxide nano-sheet electrocatalyst.
2. The method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature rise and drop according to claim 1, wherein in step 1), WO 3 nano-sheets uniformly distributed on carbon paper nano-fibers are grown in situ by a one-step hydrothermal method, and the specific operations are as follows:
step 1: mixing H 2WO4 powder with hydrogen peroxide solution, heating and stirring for reaction until a uniform transparent solution is obtained, and cooling for later use;
Step 2: and carrying out hydrothermal preparation on the uniform transparent solution, hydrochloric acid and acid-treated carbon paper to obtain the WO 3 nano-sheet grown on the carbon paper in situ.
3. The method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature rise and drop according to claim 2, wherein in step 1, the dosage ratio of H 2WO4 powder to hydrogen peroxide solution is (1-1.5) g:40mL, heating temperature is 80-100 ℃, and stirring reaction time is 2-4 h; the mass concentration of the hydrogen peroxide solution is 10-15%.
4. The method for preparing IrW oxide nanoplatelet electrocatalyst by electrodeposition in combination with rapid temperature increase and decrease according to claim 2, wherein step2 is specifically performed as follows:
Adding anhydrous sodium sulfate, concentrated hydrochloric acid and a piece of carbon paper into the uniform transparent solution, reacting for 12 hours at 180-200 ℃, naturally cooling to room temperature, taking out the carbon paper, cleaning and drying to obtain the WO 3 nano-sheet growing on the carbon paper in situ.
5. The method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature increase and decrease according to claim 4, wherein the dosage ratio of homogeneous transparent solution, anhydrous sodium sulfate and concentrated hydrochloric acid is 40mL: (0.3-0.5) g:250 μl; the carbon paper used was 2cm by 3mm in size.
6. The method for preparing IrW oxide nano-sheet electrocatalyst by combining electrodeposition with rapid temperature rise and drop according to claim 1, wherein the voltage parameter of the joule heating rapid temperature rise and drop furnace is set to 30V, the current setting parameter is 80A, the arrival temperature is 1580K, the temperature rise time is 0.25s, and the temperature drop time is 0.75s.
7. The IrW oxide nano-sheet electrocatalyst prepared by the method of any one of claims 1 to 6, characterized in that the IrW oxide nano-sheet electrocatalyst stabilizes the electrolytic water oxygen evolution reaction for more than 30 hours under the acidic condition.
8. Use of IrW oxide nanoplatelets electrocatalyst according to claim 7 for electrocatalytic decomposition of water to oxygen reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211493924.0A CN115716657B (en) | 2022-11-25 | 2022-11-25 | IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211493924.0A CN115716657B (en) | 2022-11-25 | 2022-11-25 | IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115716657A CN115716657A (en) | 2023-02-28 |
| CN115716657B true CN115716657B (en) | 2024-05-24 |
Family
ID=85256520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211493924.0A Active CN115716657B (en) | 2022-11-25 | 2022-11-25 | IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115716657B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118477698A (en) * | 2024-07-09 | 2024-08-13 | 中国科学技术大学 | Method for preparing noble metal loaded metal oxide electrocatalyst in ultra-fast way |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008959A (en) * | 2010-12-30 | 2011-04-13 | 上海大学 | Method for preparing nano-silver loaded tungsten trioxide with high photocatalytic activity |
| CN113003944A (en) * | 2021-03-31 | 2021-06-22 | 天津城建大学 | Preparation method of tungsten oxide/ammonium molybdate composite film for electrochromism |
-
2022
- 2022-11-25 CN CN202211493924.0A patent/CN115716657B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008959A (en) * | 2010-12-30 | 2011-04-13 | 上海大学 | Method for preparing nano-silver loaded tungsten trioxide with high photocatalytic activity |
| CN113003944A (en) * | 2021-03-31 | 2021-06-22 | 天津城建大学 | Preparation method of tungsten oxide/ammonium molybdate composite film for electrochromism |
Non-Patent Citations (2)
| Title |
|---|
| IrW体系电催化材料的制备及其酸性分解水性能的研究;贺敏;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑;第2021卷(第8期);34-51 * |
| WO3/贵金属复合薄膜的光电性能研究;赵一铭;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑;第2021卷(第2期);23 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115716657A (en) | 2023-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN113430553B (en) | Double-function catalytic electrode based on transition metal heterogeneous layered structure and preparation method thereof | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113445072A (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| Fu et al. | Synthesis of Pd/TiO2 nanotubes/Ti for oxygen reduction reaction in acidic solution | |
| CN113136597B (en) | Copper-tin composite material and preparation method and application thereof | |
| CN113512737B (en) | Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof | |
| CN115716657B (en) | IrW oxide nano-sheet electrocatalyst, electrodeposition combined rapid temperature rise and fall preparation method and application | |
| Cheng et al. | Pd nanofilm supported on C@ TiO2 nanocone core/shell nanoarrays: a facile preparation of high performance electrocatalyst for H2O2 electroreduction in acid medium | |
| CN114293201A (en) | Preparation method of nickel-iron catalyst for hydrogen production by water electrolysis | |
| CN110404540B (en) | Preparation method of hollow-out iron-selenium derivative catalyst, product and application thereof | |
| Zhang et al. | Robust and hydrophilic Mo-NiS@ NiTe core-shell heterostructure nanorod arrays for efficient hydrogen evolution reaction in alkaline freshwater and seawater | |
| CN110943231A (en) | Preparation method of porous nano Co @ nitrogen-carbon composite carbon felt | |
| CN113846346A (en) | Composite material, preparation method thereof and method for preparing hydrogen by electrocatalytic hydrolysis | |
| CN110391428A (en) | Self-supporting nanoporous Mo/Mo2N@Ni3Mo3N composite material and preparation method and application | |
| CN111118540B (en) | Preparation method and application of cobalt phosphate modified carbon fiber composite electrode material | |
| KR102180882B1 (en) | Synthesis method of water electrolysis catalyst using ultrasonic spray pyrolysis | |
| CN114956019B (en) | Method for one-step synthesis of cobalt phosphide by molten salt mediation and application thereof | |
| CN114614025B (en) | Structure and manufacturing method of manganese oxide reduction catalyst | |
| CN117568847B (en) | Oxygen evolution electrode loaded with ferronickel layered double hydroxide and preparation method thereof | |
| CN114808005B (en) | Nickel-iron bimetallic phosphide electrode material with two-dimensional lamellar structure, preparation method thereof and application thereof in hydrogen production by water electrolysis | |
| CN118422267B (en) | Preparation method of ferrosulfur doped nickel hydroxide electrocatalyst and electrocatalyst | |
| CN115233232A (en) | Method for preparing out-phase molybdenum carbide by one-step molten salt electrolysis method and product thereof | |
| CN118480798A (en) | High entropy FeCoNiCuMoOx/NiFeSyPreparation method of/CC amorphous alloy composite catalytic electrode | |
| CN117254041A (en) | Preparation and forming method of vanadium electrolyte electrolytic electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |