CN118186475A - Preparation method of gas diffusion electrode with micro-nano layered multi-stage structure - Google Patents
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Abstract
A preparation method of a gas diffusion electrode with a micro-nano layered multi-stage structure comprises the following steps: the preparation method of the material is simple, good in repeatability, green and nontoxic in raw materials, rich in resources and good in practical value and application prospect.
Description
Technical Field
The invention relates to the technical field of development of an electrocatalytic reduction carbon dioxide multilayer structure integrated gas diffusion electrode, in particular to a preparation method and application of a multilayer structure (comprising a gas diffusion layer, a metal conducting layer, a porous catalytic layer and a micro-nano porous ionomer modification layer) composite integrated gas diffusion electrode.
Background
In order to solve the problem, electrochemical reduction of carbon dioxide is one of effective solutions, not only is helpful for reducing the concentration of carbon dioxide, but also can be combined with renewable electric energy for use to be converted into value-added chemicals, and has certain economic value.
Products of electrochemical reduction of carbon dioxide are numerous, including carbon monoxide (CO), methane (CH 4), ethylene (C 2H4), formic acid (HCOOH), ethanol (C 2H5 OH), and the like. The electrochemical method is used for directly preparing pure formic acid, carbon monoxide, ethylene and the like with high selectivity and high energy efficiency under high current density, can realize the conversion of carbon dioxide gas into high-value carbon-containing chemicals by a one-step method, and has higher economic and technical feasibility.
The use of gas diffusion electrodes in Membrane Electrodes (MEA) can achieve direct electrocatalytic reduction of carbon dioxide, but the method still faces problems of poor catalyst stability (less than 100 hours) and low reaction energy efficiency (less than 20% energy efficiency) and poor product selectivity (less than 80% carbon monoxide, less than 70% formic acid, and less than 60% ethylene) due to flooding at higher current densities. The main reasons for this problem are the defects in the structure of the gas diffusion electrode in the MEA and the insufficient reactivity of the catalyst.
In view of this, by constructing a micro-nano scale layered structure: the catalyst material of the catalytic center is nanocrystallized, so that the key cations are locally enriched; the nano catalytic material is connected with the metal conducting layer, so that the overall conductivity of the electrode is ensured; the catalytic material is integrally connected with a Polytetrafluoroethylene (PTFE) gas diffusion layer to ensure stable construction of a three-phase interface, thereby being beneficial to realizing heavy current reaction; the ionomer layer on the surface is uniformly covered to ensure the regulation and control of local microenvironment. The integrated gas diffusion electrode with large area and controllable surface physical and chemical properties can effectively adjust the adsorption model and adsorption energy of carbon dioxide molecules on the surface of the electrode, realize high performance of electrocatalytic reduction of carbon dioxide, including high current density, high selectivity, high energy efficiency, long stability and the like, and provide possibility for industrial development of the technology. For this purpose, a corresponding technical solution needs to be designed to solve.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a preparation method of a gas diffusion electrode with a micro-nano layered multi-stage structure, which effectively solves the problems mentioned in Beijing in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: the invention discloses a preparation method of a gas diffusion electrode with a micro-nano layered multi-level structure, which comprises the following steps: s1, depositing conductive metal Y on a substrate with a gas diffusion layer by a physical method thermal evaporation coating or magnetron sputtering to form Y-PTFE;
s2, depositing a main catalyst X on Y-PTFE by a physical method thermal evaporation coating or magnetron sputtering to form a porous catalytic layer;
S3, covering an ionomer modification layer on the surface of the catalyst by a physical or chemical method, wherein the ionomer modification layer comprises silicon dioxide (SiO 2), silicon carbide (SiC) and carbon (C), and a porous multi-layer electrode structure of the bimetallic thin film is formed, so that the catalytic electrode with high activity, high selectivity and high stability is prepared.
Preferably, the conductive metal Y is copper (Cu), silver (Ag) and gold (Au).
Preferably, the conductive metal Y is selected from Cu and Ag, a metal target with purity higher than 99.9% is used as a metal source Cu and Ag, a solid porous film is formed on a substrate by deposition, and sputtering conditions of the metal Cu target and the Ag target are as follows: in a vacuum environment lower than 5 multiplied by 10 -4 Pa, the sputtering time and the power of the metal target determine the thickness and the density of the corresponding metal film layer by adopting a direct current magnetron sputtering mode.
Preferably, the main catalyst X includes bismuth (Bi), tin (Sn), lead (Pb), silver (Ag), and alloys thereof.
Preferably, the metal material selected by the main catalyst X is Bi or Ag 3 Sn, the metal sources Bi, ag and Sn are particles with the purity of more than 99.9 percent, the particles are arranged in an evaporation boat (tungsten boat), and a metal porous film is formed on a conductive substrate by deposition; the heating evaporation conditions of the metal Bi are as follows: in a vacuum environment of less than 5X 10 -4 Pa, the deposition rate isThe heating evaporation conditions of the metals Ag and Sn are as follows: in a vacuum environment of less than 5X 10 -4 Pa, the deposition rates are/>, respectivelyAnd/>
Preferably, the thickness of the catalyst layer is monitored by a crystal oscillator sheet in the deposition process, after the preparation is finished, the thickness of the catalyst layer is measured by a thickness measuring instrument such as a film thickness meter, the evaporation rate and time of metal determine the deposition thickness and the compactness of the metal film, and the structure and the proportion of the layered catalyst can be adjusted by adjusting corresponding parameters.
Preferably, the ionomer finishing layer is silicon dioxide SiO 2 and silicon carbide SiC, nano silicon dioxide or silicon carbide powder is used, the nano silicon dioxide or silicon carbide powder is dispersed in methanol solution, naphthol solution is added, the load is 10mg cm -2, and the gas diffusion electrode with a multi-layer porous structure is formed by spraying on the surface of the catalyst.
The beneficial effects are that: 1. the metal material selected by the invention has rich reserves, is green and nontoxic.
2. The method adopted by the invention has good repeatability and can be prepared in a large scale.
3. The multilayer porous electrode prepared by the invention can avoid the problem of flooding, has good stability and can realize the stability for hundreds of hours.
4. The layered electrode structure prepared by the invention can be used for preparing formic acid by electrocatalytic reduction of carbon dioxide, and the Faraday efficiency of the formic acid is more than 80% under the high current density of 50-300 mA cm –2; has good practical value and application prospect.
5. The material prepared by the invention can work in acid electrolyte, and realizes full cell potential 3V in MEA, and under the current density of 100mA cm –2, the full cell energy efficiency conversion efficiency of formic acid reaches 40%, and the concentration of formic acid can reach 1.5M.
6. The material prepared by the invention can work in acid electrolyte, and realizes full cell potential of 2V in a flow cell, and the selectivity of formic acid exceeds 90% at current density of 100mA cm –2.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of a micro-nano multi-level layered electrode prepared by the invention;
FIG. 2 is a scanning electron microscope image of a representative SiO 2 -Bi-Cu-PTFE micro-nano multi-level layered electrode prepared according to the present invention;
FIG. 3 is a diagram of an energy spectrum analysis of a representative SiO 2 -Bi-Cu-PTFE micro-nano multi-level layered electrode prepared by the invention;
FIG. 4 is a graph of the full cell potential of a representative SiO 2 -Bi-Cu-PTFE micro-nano multi-level layered electrode and a single metal catalyst Bi prepared according to the present invention at different current densities;
FIG. 5 is a graph of Faraday efficiencies of a representative SiO 2 -Bi-Cu-PTFE micro-nano multi-level layered electrode and a single metal catalyst Bi prepared according to the present invention, formic acid at different current densities;
FIG. 6 is a scanning electron microscope image of a representative SiC-Ag 3 Sn-Ag-PTFE micro-nano multi-level layered electrode prepared according to the present invention;
FIG. 7 is a diagram of an energy spectrum analysis of a representative SiC-Ag 3 Sn-Ag-PTFE micro-nano multi-level layered electrode prepared by the invention;
FIG. 8 is a graph of potentials of a representative SiC-Ag 3 Sn-Ag-PTFE micro-nano multi-level layered electrode and a catalyst Ag 3 Sn-PTFE prepared according to the present invention at different current densities;
FIG. 9 is a graph of Faraday efficiencies of representative SiC-Ag 3 Sn-Ag-PTFE micro-nano multi-level layered electrodes and catalyst Ag 3 Sn-PTFE formic acid prepared according to the present invention at different current densities.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to FIGS. 1-9.
In the first embodiment, as shown in fig. 1-9, the present invention provides a method for preparing a gas diffusion electrode with a micro-nano layered multi-stage structure, and a method for preparing a SiO 2 -Bi-Cu-PTFE multi-layer porous metal electrode, which comprises the following steps:
s1, a metal Cu target is placed below a PTFE substrate through a physical method including thermal evaporation coating or magnetron sputtering; adopting a direct current magnetron sputtering mode, depositing Cu element on the surface of a PTFE substrate to form a solid porous film, named as a Cu-PTFE conductive substrate,
In step S1, the dc magnetron sputtering conditions of the Cu target are: in a vacuum environment of less than 5X 10 –4 Pa, 150W is sputtered at constant power for 1h.
Further, the sputtering power determines the densification degree and deposition rate of the Cu thin film, and the conductivity of Cu as a conductive substrate can be affected by adjusting the power.
S2, thermally evaporating by a physical method, placing metal Bi particles in an evaporation boat (tungsten boat), and placing under the Cu-PTFE conductive substrate prepared in the step S1; heating the Bi metal to vaporize the Bi metal, and depositing the Bi metal on a Cu-PTFE conductive substrate to form a solid bimetal layered film, thereby obtaining a Bi-Cu-PTFE bimetal layered electrode;
In step S2, the metal Bi heating evaporation conditions are: in a vacuum environment of less than 5X 10 –4 Pa, current 80A, deposition rate
S3, uniformly spraying the silicon dioxide nano powder uniformly dispersed in methanol on the surface of the Bi-Cu-PTFE bimetal layered electrode prepared in the S2 by a physical method (spraying) to form an ion diffusion layer, so as to obtain the SiO 2 -Bi-Cu-PTFE multilayer porous electrode;
In step S3, the amount of silica added was 10mg/cm 2, and a 5% mass fraction of naphthol solution of 10. Mu.L/cm 2 was added.
Further, the thickness of the prepared electrode is monitored by a crystal oscillator sheet in the deposition process, and the thickness of the prepared electrode is between 500 and 1500 nm.
Further, the deposition rate of the metal Bi can influence the morphology of the catalyst surface, and the micro-nano structure of the catalyst surface can be controlled by adjusting the deposition rate.
Further, preferably, the deposition rate of the metal Bi is controlled to
Fig. 2 is an SEM image (not including a surface ion diffusion layer) of the SiO 2 -Bi-Cu-PTFE multilayer porous electrode produced in this example, and it can be seen from fig. 2 that the SiO 2 -Bi-Cu-PTFE multilayer porous electrode is tightly packed to form a porous-containing film.
Fig. 3 is an EDS image of the SiO 2 -Bi-Cu-PTFE multilayer porous electrode produced in this example (without the surface ion diffusion layer), and it can be seen from fig. 3 that the Bi metal atoms on the surface of the SiO 2 -Bi-Cu-PTFE multilayer porous electrode do not alloy with the Cu metal atoms below the surface.
Experimental example 1
The difference in catalytic activity between a SiO 2 -Bi-Cu-PTFE multilayer porous electrode and a single metal Bi electrode was understood by the following experiment.
In the experiment, a membrane electrode electrolytic tank is adopted, a Bi-PTFE single metal electrode is formed on a PTFE substrate by adopting a SiO 2 -Bi-Cu-PTFE multilayer porous electrode prepared by the method in the embodiment 1 and a thermal evaporation coating method as a working electrode (the area is 2 multiplied by 2 cm), a metal titanium felt loaded with iridium oxide is used as a counter electrode, a constant current working mode is adopted, and the current interval is 50-300mA cm –2.
In the above experimental method, the gas flow rate of CO 2 was 30sccm, and the electrolyte used for the anode was 0.5M H 2SO4.
Through the above experimental method, the full cell potential curves at different current densities are shown in fig. 4, which shows that the reaction potential of the SiO 2 -Bi-Cu-PTFE multi-layer porous electrode has obvious advantages compared with that of another material.
Through the experimental method, the formic acid Faraday efficiency of the porous electrode under different current densities is shown as figure 5, which shows that the SiO 2 -Bi-Cu-PTFE multi-layer porous electrode can still maintain the formic acid Faraday efficiency of more than 80% under larger current densities; in addition, the full cell energy efficiency of the SiO 2 -Bi-Cu-PTFE multilayer porous electrode was superior to that of the Bi-PTFE comparative electrode at each current density. The SiO 2 -Bi-Cu-PTFE multilayer porous electrode has good selectivity and catalytic activity to formic acid.
Experimental example two
The improvement of the performance of the gas diffusion electrode structure with the stacked multi-layer structure (comprising a gas diffusion layer, a porous metal conducting layer, a porous catalytic layer and an ion diffusion layer) to the metallographic catalyst is known through the following experiment.
The experiment adopts a flow cell electrolytic tank, and the specific preparation method is as follows:
S1, placing a metal Ag target below a PTFE substrate by a physical method (including thermal evaporation coating, magnetron sputtering and the like); and depositing Ag element on the surface of the PTFE substrate by adopting a direct current magnetron sputtering mode to form a solid porous film, which is named as an Ag-PTFE conductive substrate.
In step S1, the conditions of the dc magnetron sputtering of the Ag target are: in a vacuum environment of less than 5X 10 –4 Pa, 100W is sputtered at constant power for 1h.
Further, the sputtering power determines the densification degree and deposition rate of the Ag thin film, and the conductivity of Ag as a conductive substrate can be affected by adjusting the power.
S2, respectively placing metal Ag particles and Sn particles in an evaporation boat (tungsten boat) by a physical method (thermal evaporation), and placing under the Ag-PTFE conductive substrate prepared in the step S1; and heating the metal Ag and Sn to vaporize, and depositing on the Ag-PTFE conductive substrate to form an Ag 3 Sn alloy phase without phase separation and form a solid bimetal layered film to obtain the Ag 3 Sn-Ag-PTFE bimetal layered electrode.
In step S2, the metal Ag is heated and evaporated under the following conditions: in a vacuum environment of less than 5X 10-4Pa, current 180A, deposition rateThe metal Sn heating evaporation conditions are as follows: in a vacuum environment of less than 5X 10 –4 Pa, current 120A, deposition rate/>Both metals are evaporated simultaneously and their rate ratio is controlled to be equal to the mass ratio of the substances.
S3, uniformly spraying silicon carbide nano powder uniformly dispersed in methanol on the surface of the Ag 3 Sn-Ag-PTFE bimetal layered electrode prepared in S2 by a physical method (spraying) to form an ion diffusion layer, thereby obtaining the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode
In step S3, silicon carbide was added in an amount of 10mg/cm 2, and a 5% mass fraction of naphthol solution of 10. Mu.L/cm 2 was added.
Further, the thickness of the prepared electrode is monitored by a crystal oscillator sheet in the deposition process, and the thickness of the prepared electrode is between 500 and 1500 nm.
Further, the deposition rate of the metal Ag and the metal Sn can influence the appearance of the surface of the catalyst, and the micro-nano structure of the surface of the catalyst can be controlled by adjusting the deposition rate.
Further, it is preferable that the total deposition rate of the metal Ag and the metal Sn is controlled to
Fig. 6 is an SEM image (not including a surface ion diffusion layer) of the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode produced in this example, and it can be seen from fig. 6 that the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode is tightly packed to form a porous-containing film.
Fig. 7 is an EDS image (not including the surface ion diffusion layer) of the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode produced in this example, and it can be seen from fig. 3 that the metal atoms Ag and the metal atoms Sn form an alloy phase and no phase separation at the surface of the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode.
By using the conditions in S2, a gas diffusion electrode Ag 3 Sn-PTFE containing only the alloy catalyst layer was separately prepared as a comparison.
The multi-layer porous electrode of SiC-Ag 3 Sn-Ag-PTFE prepared by the method in this example and the thermal evaporation plating method were each used to form Ag 3 Sn-PTFE metal electrode as a working electrode (area 1 x 1 cm) on a PTFE substrate. The counter electrode uses a metal titanium felt loaded with iridium oxide, the reference electrode is Ag/AgCl, a constant current working mode is adopted, and the current interval is 100-800mA cm –2.
In the above experimental method, the gas flow rate of CO 2 was 30sccm, the electrolyte used for the anode was 0.5: 0.5M H 2SO4, and the electrolyte used for the cathode was 3M KCl solution with pH=1
Through the above experimental method, the full cell potential curves at different current densities are shown in fig. 8, which shows that the reaction potential of the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode has a significant advantage over another material.
Through the experimental method, the formic acid Faraday efficiency of the porous electrode under different current densities is shown as figure 9, which shows that the SiC-Ag 3 Sn-Ag-PTFE multi-layer porous electrode can still maintain the formic acid Faraday efficiency of more than 90% under larger current densities; in addition, the full cell energy efficiency of the SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode was superior to that of the Bi-PTFE comparative electrode at each current density. The SiC-Ag 3 Sn-Ag-PTFE multilayer porous electrode has good selectivity and catalytic activity to formic acid.
The beneficial effects are that: 1. the metal material selected by the invention has rich reserves, is green and nontoxic.
2. The method adopted by the invention has good repeatability and can be prepared in a large scale.
3. The micro-nano multi-stage layered electrode prepared by the method can avoid the problem of flooding, has good stability and can realize the stability for hundreds of hours.
4. The layered electrode structure prepared by the invention can be used for preparing formic acid by electrocatalytic reduction of carbon dioxide, and the Faraday efficiency of the formic acid is more than 80% under the high current density of 50-300 mA cm –2; has good practical value and application prospect.
5. The material prepared by the invention can work in acid electrolyte, and realizes full cell potential 3V in MEA, and under the current density of 100mA cm –2, the full cell energy efficiency conversion efficiency of formic acid reaches 40%, and the concentration of formic acid can reach 1.5M.
6. The material prepared by the invention can work in acid electrolyte, and realizes full cell potential of 2V in a flow cell, and the selectivity of formic acid exceeds 90% at current density of 100mA cm –2.
The main catalyst metal X prepared by the application of the bimetallic material catalyst comprises bismuth (Bi), tin (Sn), lead (Pb), silver (Ag), alloys thereof and the like, and conductive metals comprising copper (Cu), silver (Ag), gold (Au) and the like, wherein the micro-nano multi-level layered structure electrode is formed by depositing the materials on a substrate such as a gas diffusion electrode and the like and spraying an ion diffusion layer for electrocatalytic.
Application of layered electrode the prepared SiO 2 -Bi-Cu-PTFE and SiC-Ag 3 Sn-Ag-PTFE layered gas diffusion electrode is used for electrocatalysis.
The application of the bimetallic material catalyst is that the prepared SiO 2 -Bi-Cu-PTFE and SiC-Ag 3 Sn-Ag-PTFE micro-nano multi-level layered electrode is used for preparing at least one carbon product by electrocatalytic reduction of carbon dioxide; the electrocatalytic process may be carried out in an acidic electrolyte environment.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the gas diffusion electrode with the micro-nano layered multi-stage structure is characterized by comprising the following steps of: the method comprises the steps of depositing conductive metal Y on a substrate with a gas diffusion layer through a physical method, wherein the substrate comprises a Polytetrafluoroethylene (PTFE) substrate or a carbon paper substrate, forming a conductive metal layer, then depositing a main catalyst X on the porous conductive metal layer through a physical method, forming a porous metal catalytic layer, and finally forming a micro-nano porous ion diffusion layer on the surface of the catalyst through a physical or chemical method, wherein the micro-nano porous ion diffusion layer comprises silicon dioxide (SiO 2), silicon carbide (SiC) and carbon (C), so that a multi-layer metal/protective material film electrode structure is formed.
2. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 1, wherein the method comprises the following steps: the conductive metal Y is copper (Cu), silver (Ag) and gold (Au).
3. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 1, wherein the method comprises the following steps: the conductive metal Y is selected from Cu and Ag, a metal target with purity of more than 99.9% is used as a metal source Cu and Ag, a solid porous film is formed on a substrate by deposition, and sputtering conditions of the metal Cu target and the Ag target are as follows: in a vacuum environment lower than 5 multiplied by 10 -4 Pa, the sputtering time and the power of the metal target determine the thickness and the density of the corresponding metal film layer by adopting a direct current magnetron sputtering mode.
4. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 1, wherein the method comprises the following steps: the main catalyst X includes bismuth (Bi), tin (Sn), lead (Pb), silver (Ag) and alloys thereof.
5. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 1, wherein the method comprises the following steps: the metal material selected by the main catalyst X is Bi or Ag 3 Sn, the metal sources Bi, ag and Sn are particles with the purity of more than 99.9 percent, the particles are arranged in an evaporation boat (tungsten boat), and a metal porous film is formed on a conductive substrate by deposition; the heating evaporation conditions of the metal Bi are as follows: in a vacuum environment of less than 5X 10 -4 Pa, the deposition rate isThe heating evaporation conditions of the metals Ag and Sn are as follows: in a vacuum environment of less than 5X 10 -4 Pa, the deposition rates are/>, respectivelyAnd/>
6. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 5, wherein the method comprises the following steps: the thickness of the catalyst layer is monitored by a crystal oscillator plate in the deposition process, after the preparation is finished, the thickness of the catalyst layer is measured by a thickness measuring instrument such as a film thickness meter, the evaporation rate and time of metal determine the deposition thickness and the density of a metal film, and the structure and the proportion of the layered catalyst can be adjusted by adjusting corresponding parameters.
7. The method for preparing the gas diffusion electrode with the micro-nano layered multi-stage structure according to claim 1, wherein the method comprises the following steps: the ionomer modifying layer is silicon dioxide SiO 2 and silicon carbide SiC, nano silicon dioxide or silicon carbide powder is used, the nano silicon dioxide or silicon carbide powder is dispersed in methanol solution, naphthol solution is added, the load is 10mg cm -2, and the nano silicon dioxide or silicon carbide powder is sprayed on the surface of the catalyst to form a multi-layer gas diffusion electrode containing a porous structure.
8. Use of an electrode structure according to any of claims 1-7, characterized in that: the prepared porous conductive metal layer and porous catalytic layer comprise a multi-layer porous metal electrode formed by depositing bimetallic materials of any two of bismuth (Bi), tin (Sn), lead (Pb), copper (Cu), silver (Ag), gold (Au) and the like on a diffusion gas electrode substrate for electrocatalytic.
9. Use of an electrode according to claim 8, characterized in that: the prepared SiO 2 -Bi-Cu-PTFE multilayer porous electrode is used for electrocatalysis.
10. Use of an electrode according to claim 8, characterized in that: the prepared SiO 2 -Bi-Cu-PTFE multilayer porous electrode is used for preparing at least one single carbon product by electrocatalytic reduction of carbon dioxide; the electrocatalytic process may be carried out in an acidic electrolyte.
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