CN111118550B - Al-Ni nanocrystalline porous material prepared from aluminum-based alloy, and preparation method and application thereof - Google Patents

Al-Ni nanocrystalline porous material prepared from aluminum-based alloy, and preparation method and application thereof Download PDF

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CN111118550B
CN111118550B CN201811277468.XA CN201811277468A CN111118550B CN 111118550 B CN111118550 B CN 111118550B CN 201811277468 A CN201811277468 A CN 201811277468A CN 111118550 B CN111118550 B CN 111118550B
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朱胜利
周奕扬
崔振铎
杨贤金
井上明久
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Tianjin University
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Abstract

The invention provides an Al-Ni nanocrystalline porous material prepared by aluminum-based alloy, a preparation method and application thereof, firstly preparing Al-Ni original alloy; cutting the Al-Ni alloy into Al-Ni alloy strips, ultrasonically cleaning the Al-Ni alloy strips in absolute ethyl alcohol, cleaning the Al-Ni alloy strips with deionized water, and drying the Al-Ni alloy strips for later use; and placing the strip and a potassium hydroxide solution into an electrolytic bath together for electrochemical reaction, and washing and drying a sample prepared after the reaction is finished to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy. The specific surface area is large, the catalytic activity of the electrolytic water is high, the implementation cost is low, the operation is simple and convenient, the time consumption is short, and the method is a high-efficiency and economical synthesis method.

Description

Al-Ni nanocrystalline porous material prepared from aluminum-based alloy, and preparation method and application thereof
Technical Field
The invention relates to the technical field of nanocrystalline porous materials, in particular to an Al-Ni nanocrystalline porous material prepared from an aluminum-based alloy, and a preparation method and application thereof.
Background
In recent years, hydrogen energy has received increasing attention in the field of new energy due to its high transduction efficiency and cleanliness without pollution. However, anode catalyst activity and cost issues have been limiting the large scale application of direct hydrogen energy. So far, Pt and its alloy show the most excellent performance in the field of hydrogen production by electrolysis, but the expensive price and limited reserves limit the commercial application of Pt and its alloy catalyst. Therefore, researchers are focusing on finding a low-cost, high-efficiency electrolytic water catalyst to improve the commercial practicability of the catalyst. Research shows that some specific crystal faces of the Al-Ni intermetallic compound can be used as active sites of hydrogen evolution reaction and have stronger catalytic activity. In addition, the Al-Ni alloy has larger practical application value as a non-noble metal element.
The phase diagram of the Al-Ni binary alloy shows that various types of alloy phases (such as Al) exist in the alloy system3Ni,Al3Ni2AlNi, etc.). The hydrogen binding energy of the catalyst surface is an important index for measuring the activity of the catalyst, and when the hydrogen binding energy of the catalytic material surface is close to zero, the bonding bond strength between the catalyst and H is proper. Calculated, Al3Ni2The (100) crystal face of (A) has a suitable hydrogen binding energy, which can be used as an active site for hydrogen evolution reaction in the catalyst. In contrast, Al3Ni (010) crystal face hydrogen bonding energy is relatively negative, namely bonding strength of the crystal face and H is too high, and surface reconstruction phenomenon is generated when H is adsorbed on the surface of the material, so that Al3Ni is an inactive phase of an Al-Ni alloy system in the field of electrolysis water hydrogen evolution catalysis. In addition, as can be seen from the phase diagram of the Al-Ni binary alloy, Al is not easily obtained by the conventional heat treatment method3Ni2The electrochemical dealloying method can dissolve Al atoms from the Al-rich compound phase by controlling the loading potential and the reaction time in the dealloying process, thereby obtaining Al with high catalytic activity of electrolyzing water to separate hydrogen3Ni2And (4) phase(s). The composition of the phase in the product can be controlled by controlling the components of the original alloy and the dealloying reaction conditions, and the NiO phase generated after dealloying can greatly improve the catalytic performance of the hydrogen evolution reaction. In addition, grain size is an important factor affecting the kinetics of catalytic reactions, and smaller grain sizes can expose more reactive sites and thus improve the catalytic performance of the material. The dissolution and structural reorganization of atoms on the surface of the material during the dealloying process can enable the catalyst to generate a nanocrystalline structure. By simultaneous dealloyingThe porous Al-Ni catalyst is prepared, so that the specific surface area of the material is greatly increased, the active sites are exposed more fully, and the overall catalytic activity of the material is improved. Therefore, the Al-Ni nanocrystalline porous catalyst prepared by a proper method can reduce the cost of the water electrolysis hydrogen production catalyst to the maximum extent and increase the applicability of the catalyst.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides an Al-Ni nanocrystalline porous material prepared from an aluminum-based alloy, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme.
The Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy and the preparation method thereof are carried out according to the following steps:
step 1, preparing an Al-Ni original alloy according to the following components and atomic percentage content: the Al content is 55-98%, and the Ni content is 2-45%;
step 2, cutting the Al-Ni original alloy prepared in the step 1 into strips with the thickness of 8-32 mu m, the width of 1-3mm and the length of 1-3cm, placing the strips in absolute ethyl alcohol, carrying out ultrasonic treatment for 3-8min, cleaning with deionized water, and drying in the air to obtain Al-Ni original alloy strips;
and 3, placing the Al-Ni original alloy strip prepared in the step 2 and a potassium hydroxide solution with the molar concentration of 0.6-1.5M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.50-0.70V, the reaction time is 8-20min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
In step 1, the Al-Ni original alloy contains 60-95% of Al and 5-40% of Ni.
In step 2, the Al-Ni original alloy strip has the thickness of 10-30 μm, the width of 2mm and the length of 2cm, and is placed in absolute ethyl alcohol for ultrasonic treatment for 4-6 min.
In step 3, the molar concentration of the potassium hydroxide solution is 0.8-1.2M, the dealloying potential is-0.55-0.65V, and the reaction time is 10-18 min.
The Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy is applied to a catalyst material for producing hydrogen by electrolyzing water.
The invention has the beneficial effects that: the porous material prepared by the dealloying method has high specific surface area, good conductivity and high structural stability and can promote the material transmission. The adoption of proper electrochemical dealloying condition can make Al-Ni alloy system produce large quantity of Al3Ni2And the (100) crystal face of the phase can be used as an active site for the hydrogen evolution reaction of electrolysis water, so that the material has stronger catalytic activity. Compared with other alloys, the Al-Ni porous nanocrystalline material prepared by the electrochemical dealloying method has extremely fine grain size, and the nanocrystalline structure can provide more catalytic active sites and greatly improve the catalytic performance of the material from the reaction kinetics perspective. Meanwhile, the NiO phase obtained in the dealloying process can generate a synergistic effect with other active phases, so that the improvement of hydrogen evolution performance is promoted. The Al-Ni porous nanocrystalline material prepared by the electrochemical dealloying method has low production cost, higher economic benefit and stable surface structure and chemical property. In the linear sweep voltammetry test, the current density of electrocatalytic hydrogen production is 10mA cm-2When the overvoltage is measured, the overpotential can reach 45mV to 92 mV.
Drawings
FIG. 1 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 1;
FIG. 2 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 2;
FIG. 3 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 3;
FIG. 4 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 4;
FIG. 5 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 5;
FIG. 6 is an SEM image of the nanoporous structure of the surface of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 6;
FIG. 7 is a linear sweep voltammogram of a nanoporous structure on the surface of Al-Ni nanocrystalline porous materials prepared from each of the aluminum-based alloys prepared in examples 1-6;
FIG. 8 is an XRD phase calibration diagram of Al-Ni nanocrystalline porous materials prepared from aluminum-based alloys prepared in examples 1,2 and 3.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 85-95%, and the Ni content is 5-15%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 10-30 μm, the width of 2mm and the length of 2 cm; ultrasonically treating the strip in absolute ethyl alcohol for 5min, cleaning the strip in deionized water, and drying the strip in air for later use;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.8-1.2M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.55V-0.65V, the reaction time is 10min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
Fig. 1 shows an SEM image of the nanoporous structure of the surface of the Al — Ni nanocrystalline porous material prepared from the aluminum-based alloy according to example 1. The alloy material has high specific surface area, good conductivity and high stability, and can promote the material transmission, so that the hydrogen production catalyst can be produced in the electrolysis of waterHas better application prospect in the preparation field. The Al-Ni nanocrystalline catalytic material prepared by the electrochemical dealloying method has stable chemical properties of the porous structure, and a linear sweep voltammetry curve of the Al-Ni nanocrystalline porous material prepared by the aluminum-based alloy prepared in the example 1 is shown in figure 7, wherein the current density of the Al-Ni nanocrystalline porous material for electro-catalysis hydrogen production in a linear sweep voltammetry test is 10mA cm-2The overpotential was 92 mV. FIG. 8 shows the XRD phase calibration diagram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 1, wherein the phase after electrochemical dealloying is Al2O3,Al3Ni2And NiO phase.
Example 2
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 85-95%, and the Ni content is 5-15%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 10-30 mu m, the width of 1mm and the length of 1 cm; the strip is cleaned in deionized water and dried in air for standby after being subjected to ultrasonic treatment in absolute ethyl alcohol for 3 min;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.6-1.0M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.50V-0.60V, the reaction time is 18min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
FIG. 2 shows an SEM image of the porous structure of the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy prepared in example 2, and FIG. 7 shows a linear sweep voltammetry curve of the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy prepared in example 2, which shows a current density of 10mA cm for electrocatalytic hydrogen production in a linear sweep voltammetry test-2The overpotential was 86 mV.
Example 3
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 75-85%, and the Ni content is 15-25%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 8-25 mu m, the width of 3mm and the length of 3 cm; the strip is cleaned in deionized water and dried in air for standby after being subjected to ultrasonic treatment in absolute ethyl alcohol for 8 min;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.8-1.5M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.55V-0.70V, the reaction time is 8min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
FIG. 3 shows an SEM image of the porous structure of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy prepared in example 3, and FIG. 7 shows a linear sweep voltammetry curve of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy prepared in example 3, with a current density of 10mA cm for electrocatalytic hydrogen production in a linear sweep voltammetry test-2The overpotential was 45 mV. FIG. 8 shows the XRD phase calibration diagram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 3, wherein the phase after electrochemical dealloying is Al2O3,Al3Ni2And NiO phase.
Example 4
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 75-85%, and the Ni content is 15-25%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 12-32 mu m, the width of 2mm and the length of 2 cm; the strip is cleaned in deionized water and dried in air for standby after being subjected to ultrasonic treatment in absolute ethyl alcohol for 6 min;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.6-0.8M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.60V-0.68V, the reaction time is 20min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
FIG. 4 is an SEM image showing the porous structure of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 4, and FIG. 7 is a linear sweep voltammogram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 4, having a current density of 10mA cm for electrocatalytic hydrogen production in a linear sweep voltammogram test-2The overpotential was 46 mV.
Example 5
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 60-75%, and the Ni content is 25-40%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 10-30 mu m, the width of 2mm and the length of 2 cm; ultrasonically treating the strip in absolute ethyl alcohol for 4min, cleaning the strip in deionized water, and drying the strip in air for later use;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.8-0.9M into an electrolytic tank together for electrochemical reaction, wherein the dealloying potential is-0.55V-0.68V, the reaction time is 15min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
FIG. 5 is an SEM image showing the porous structure of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 5, and FIG. 7 is a linear sweep voltammogram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 5, having a current density of 1 for electrocatalytic hydrogen production in a linear sweep voltammogram test00mA cm-2The overpotential was 74 mV. FIG. 8 shows the XRD phase calibration diagram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy in example 5, wherein the phase after electrochemical dealloying is Al3Ni2,Al3Ni, NiO phase.
Example 6
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 60-75%, and the Ni content is 25-40%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 10-30 mu m, the width of 2mm and the length of 2 cm; ultrasonically treating the strip in absolute ethyl alcohol for 4min, cleaning the strip in deionized water, and drying the strip in air for later use;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.6-1.2M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.55V-0.65V, the reaction time is 12min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
FIG. 6 is an SEM image showing the porous structure of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 6, and FIG. 7 is a linear sweep voltammogram of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy obtained in example 6, having a current density of 10mA cm for electrocatalytic hydrogen production in a linear sweep voltammogram test-2The overpotential was 84 mV.
Example 7
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 55-65%, and the Ni content is 40-35%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 10-32 mu m, the width of 3mm and the length of 3 cm; the strip is cleaned in deionized water and dried in air for standby after being subjected to ultrasonic treatment in absolute ethyl alcohol for 8 min;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.8-1.5M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.55V-0.65V, the reaction time is 16min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
Example 8
The preparation method for preparing the Al-Ni nanocrystalline porous material by using the aluminum-based alloy comprises the following steps:
step 1, preparing an Al-Ni original alloy strip according to the following components and atom percentage content: the Al content is 90-98%, and the Ni content is 2-10%;
step 2, cutting the Al-Ni original alloy strip prepared in the step 1 into a strip with the thickness of 8-24 mu m, the width of 1mm and the length of 1 cm; the strip is cleaned in deionized water and dried in air for standby after being subjected to ultrasonic treatment in absolute ethyl alcohol for 3 min;
and 3, putting the Al-Ni alloy strip prepared in the step 2 and 100ml of potassium hydroxide solution with the molar concentration of 0.6-1.0M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.55V-0.65V, the reaction time is 14min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
From the above examples, it can be seen that the Al-Ni nanocrystalline material with a porous structure can be obtained according to the preparation method of the invention. The porous structure of the Al-Ni nanocrystalline catalytic material generates obvious hydrogen evolution current during a linear sweep voltammetry test, which shows that the prepared material has good application prospect in the field of hydrogen production by water electrolysis.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (8)

1. The Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy is characterized in that: the method comprises the following steps:
step 1, preparing an Al-Ni original alloy according to the following components and atomic percentage content: the Al content is 60-95%, and the Ni content is 5-40%;
step 2, cutting the Al-Ni original alloy prepared in the step 1 into strips with the thickness of 8-32 mu m, the width of 1-3mm and the length of 1-3cm, placing the strips in absolute ethyl alcohol, carrying out ultrasonic treatment for 3-8min, cleaning with deionized water, and drying in the air to obtain Al-Ni original alloy strips;
and 3, placing the Al-Ni original alloy strip prepared in the step 2 and a potassium hydroxide solution with the molar concentration of 0.6-1.5M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.50-0.70V, the reaction time is 8-20min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
2. The Al-Ni nanocrystalline porous material prepared from an aluminum-based alloy according to claim 1, characterized in that: in step 2, the Al-Ni original alloy strip has the thickness of 10-30 μm, the width of 2mm and the length of 2cm, and is placed in absolute ethyl alcohol for ultrasonic treatment for 4-6 min.
3. The Al-Ni nanocrystalline porous material prepared from an aluminum-based alloy according to claim 1, characterized in that: in step 3, the molar concentration of the potassium hydroxide solution is 0.8-1.2M, the dealloying potential is-0.55-0.65V, and the reaction time is 10-18 min.
4. A method for preparing an Al-Ni nanocrystalline porous material from an aluminium based alloy according to any of claims 1-3, characterized in that: the method comprises the following steps:
step 1, preparing an Al-Ni original alloy according to the following components and atomic percentage content: the Al content is 60-95%, and the Ni content is 5-40%;
step 2, cutting the Al-Ni original alloy prepared in the step 1 into strips with the thickness of 8-32 mu m, the width of 1-3mm and the length of 1-3cm, placing the strips in absolute ethyl alcohol, carrying out ultrasonic treatment for 3-8min, cleaning with deionized water, and drying in the air to obtain Al-Ni original alloy strips;
and 3, placing the Al-Ni original alloy strip prepared in the step 2 and a potassium hydroxide solution with the molar concentration of 0.6-1.5M into an electrolytic bath for electrochemical reaction, wherein the dealloying potential is-0.50-0.70V, the reaction time is 8-20min, washing a sample prepared after the reaction is finished with deionized water, and drying in the air to obtain the Al-Ni nanocrystalline porous material prepared from the aluminum-based alloy.
5. The method for preparing Al-Ni nanocrystalline porous material from aluminum-based alloy according to claim 4, characterized in that: in step 2, the Al-Ni original alloy strip has the thickness of 10-30 μm, the width of 2mm and the length of 2cm, and is placed in absolute ethyl alcohol for ultrasonic treatment for 4-6 min.
6. The method for preparing Al-Ni nanocrystalline porous material from aluminum-based alloy according to claim 4, characterized in that: in step 3, the molar concentration of the potassium hydroxide solution is 0.8-1.2M, the dealloying potential is-0.55-0.65V, and the reaction time is 10-18 min.
7. Use of the Al-Ni nanocrystalline porous material prepared from an aluminum-based alloy according to any one of claims 1 to 3 in a catalyst material for hydrogen production by electrolysis of water.
8. Use according to claim 7, characterized in that: when the current density of electrocatalytic hydrogen production is 10mA cm-2When in use, the overpotential of Al-Ni nanocrystalline porous material prepared from aluminum-based alloy is 45-92 mV.
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