CN115874212B - 3-D open-framework porous electrocatalyst and preparation method and application thereof - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 9
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- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 9
- 239000011565 manganese chloride Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
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- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of electrocatalysts, in particular to a 3-D open-framework porous electrocatalyst, and a preparation method and application thereof. Dissolving manganese chloride, yttrium chloride and 2,2 '-bipyridine-5, 5' -dicarboxylic acid in ultrapure water, performing hydrothermal synthesis to obtain a precursor, calcining at different temperatures to obtain a porous catalyst, and adjusting the metal proportion, the heating temperature of a reaction kettle and the calcining temperature to obtain the 3-D skeleton porous catalyst with different pore size distribution and morphology. The catalyst is evenly sprayed on commercially available conductive carbon paper to obtain a series of catalyst electrodes with different proportions. Compared with other electrocatalysts, the invention adopts a hydrothermal synthesis method and high-temperature calcination combined self-assembled porous structure, so that raw materials are easy to obtain, the synthesis method is simple and controllable, and rich rare earth resources in China can be greatly supported. The catalyst can be applied to electrocatalytic reduction of carbon dioxide to obtain high-value industrial raw material carbon monoxide, and has stable catalytic performance and high yield.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a 3-D open-framework porous electrocatalyst, and a preparation method and application thereof.
Background
Global warming and glacier thawing have attracted considerable attention due to excessive emissions of greenhouse gases such as carbon dioxide. Thus, there is an urgent need to explore effective methods to reduce CO in air 2 Is a cumulative sum of (a) and (b). CO is processed by 2 Electrocatalytic conversion into value-added products, which can reduce CO against the rapid consumption of fossil fuels 2 Concentration, and provides a promising strategy for sustainable development of global carbon balance. However, CO 2 Moderately stable c=o bond (806 kJ mol) -1 ) And competing Hydrogen Evolution Reactions (HER) in aqueous solutions severely hamper conversion efficiency and selectivity. Thus, to meet strategic applications, the CO may be facilitated by rational design of advanced electrocatalysts with atomically dispersed active sites 2 Electrochemical reduction to a value-added chemical product.
CO is essential in the chemical industry as a feedstock for value-added chemicals through existing downstream thermochemical reactions. Currently, CO 2 Electro-reduction reaction (CO) 2 RR) to produce CO, there is increasing interest in its clean production and suppression of the greenhouse effect. Electrocatalyst designed with atomically dispersed transition metal sites, in particular non-noble Fe and CO sites, is considered CO 2 A promising solution for RR production of CO due to their powerful CO 2 Activation ability. Unfortunately, the difficulty of CO desorption at transition metal sites (potential independent step) limits its CO production activity because their directional local 3d orbitals readily hybridize to the 5σ and 2π orbitals of CO. Therefore, it is of great importance to find new active sites with non-directional delocalized orbitals for CO desorption. As is known from the study, the 3s orbitals of Mn have non-directional delocalization characteristics, so that the interaction with CO is weak. On the other hand, CO 2 Can be easily activated by s-block metals, i.e. yttrium (Y) which is a rare earth element can be used as CO 2 Cofactors of RR. Therefore, there is an urgent need to develop a novel electrocatalyst for CO 2 RR, solve CO 2 Electrocatalytic reduction of high value industrial raw material CO.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a 3-D open-framework porous electrocatalyst, a preparation method and application thereof, wherein a catalyst precursor is prepared by a hydrothermal synthesis method, and carbon black is added for high-temperature calcination to obtain the electrocatalyst so as to solve CO 2 Electrocatalytic reduction to obtain high-value industrial raw material CO.
In order to solve the technical problems of the invention, the invention adopts the following technical scheme:
in order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first object of the invention is to provide a preparation method of a 3-D open-framework porous electrocatalyst, comprising the following steps:
s1, dissolving manganese chloride, yttrium chloride and 2,2 '-bipyridine-5, 5' -dicarboxylic acid in ultrapure water, mixing and stirring to obtain a catalyst precursor synthesis stock solution;
s2, transferring the catalyst precursor synthesized stock solution obtained in the step S1 into a tetrafluoroethylene reaction kettle for heating, and cooling the reaction kettle to room temperature at 10 ℃/h after heating is finished to obtain a solid-liquid mixture;
s3, centrifuging the solid-liquid mixture obtained in the step S2, cleaning the centrifugally separated solid with ultrapure water for 3-5 times, and drying to obtain a precursor of the catalyst;
s4, heating the precursor of the catalyst obtained in the step S3 and carbon black to 700-900 ℃ at a speed of 4 ℃/min under the protection of argon in a tube furnace, calcining at a high temperature for 3-5h, and cooling to room temperature at a speed of 4 ℃/min to obtain the 3-D open-framework porous electrocatalyst.
Further, in S1, the mass ratio of the manganese chloride, yttrium chloride, 2 '-bipyridine-5, 5' -dicarboxylic acid and ultrapure water is (0.4-2): (8-11): (10-14): (800-1200).
In S1, the dissolution is carried out by using ultrasonic waves for 10-20min.
Further, in the step S2, the reaction kettle is placed in an oven at 160-180 ℃ and heated for 60-80 hours.
Further, in S3, the centrifugal speed is 8000-12000rpm, and the time is 1-3min.
In the step S3, the drying is carried out by heating in a vacuum drying oven at 50-60 ℃ for 1-2h.
Further, in S4, the mass ratio of the precursor of the catalyst to the carbon black is 1:4-6.
A second object of the present invention is to provide a 3-D open-framework porous electrocatalyst.
A third object of the invention is to provide the use of a 3-D open-framework porous electrocatalyst for electrocatalytic reduction of carbon dioxide. The 3-D open-framework porous electrocatalyst is used for CO 2 RR, because of its atomic dispersion Mn-Y bimetallic catalyst with good CO 2 Activation and CO desorption capacity, thereby having superior CO 2 RR performance.
Further, commercial conductive carbon paper loaded with 3-D open-framework porous electrocatalyst is used as a working electrode, a high-purity graphite rod is used as a counter electrode, ag/AgCl is used as a reference electrode, and electrolyte is KHCO of 0.1M 3 Introducing CO into H-type electrolytic cell at constant voltage of-1.47V 2 And (5) carrying out electrolysis to obtain CO.
In an H-cell, the catalyst has a CO Faraday efficiency ((FE) CO ) =96.6%) is extremely high, shows high CO production activity, and provides wide prospect for industrial application of CO.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts hydrothermal synthesis and high-temperature calcination methods, and the manganese chloride, yttrium chloride, 2 '-bipyridine-5, 5' -dicarboxylic acid are dissolved in ultrapure water to obtain the porous material after calcination, the method is simple, the conditions are controllable, the raw materials are low in price, and abundant rare earth resources in China are fully utilized.
2. The electrocatalyst obtained by the invention is nontoxic and harmless, and has high efficiency, high selectivity and high stability when used as a catalyst.
3. According to the invention, through effectively regulating and controlling the conditions such as the concentration of raw materials in the metal solution, the time required by the high-temperature calcination process and the like, the Mn-Y-N-C catalyst with specific size is obtained. The electrocatalyst is for CO 2 The porous material has larger active specific surface area and provides rich catalytic active sites for electrochemical reduction performance. XRD shows that the prepared catalyst has no obvious characteristic peak, takes the synthesized atomic-level dispersed material as the main material, and the specific dispersion structure solves the problem of electrocatalytic CO 2 The poor selectivity in RR process obviously improves Faraday efficiency ((FE) in CO conversion process CO ) =96.6%) and has wide industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a 3-D open-framework porous electrocatalyst prepared in example 1 according to the invention;
FIG. 2 is an X-ray crystal diffraction pattern of a 3-D open-framework porous electrocatalyst prepared in example 1 according to the invention;
FIG. 3 is a linear sweep voltammogram of electrocatalytically reduced carbon dioxide in test example 1;
FIG. 4 is a graph showing CO reduction at different potentials during electrocatalytic reduction of carbon dioxide in test example 1 2 Generating a faraday efficiency map of CO;
FIG. 5 is a graph showing the stability test of electrocatalytically reduced carbon dioxide in test example 2.
Detailed Description
The experimental methods in the following examples are conventional methods unless otherwise indicated, and the raw materials and reagents according to the present invention are commercially available as usual unless otherwise indicated.
The technology and features of the present invention will be described in detail below with reference to specific examples, but these examples are not intended to limit the scope of the invention.
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings (fig. 1-5) and the detailed description.
Example 1: prepared 3-D open-framework porous electrocatalyst
A method for preparing a 3-D open-framework porous electrocatalyst, comprising the steps of:
s1, 12.6mg of manganese chloride, 97.6mg of yttrium chloride and 122.1mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are added into 10mL of ultrapure water, ultrasonic treatment is carried out for 10min until complete dissolution, and mixing and stirring are carried out, thus obtaining a catalyst precursor synthesis stock solution;
s2, transferring the catalyst precursor synthesized stock solution obtained in the step S1 into a 25mL tetrafluoroethylene reaction kettle, heating at 170 ℃ for 72 hours, and cooling the reaction kettle to room temperature at 10 ℃/h after heating is finished to obtain a solid-liquid mixture;
s3, centrifuging the solid-liquid mixture obtained in the step S2 at 10000rpm for 2min, washing the centrifugally separated solid with ultrapure water for 3 times, and drying in a vacuum drying oven at 55 ℃ to obtain a precursor of the catalyst;
s4, heating the precursor of the catalyst 10mg obtained in the step S3 and 50mg of carbon black to 800 ℃ at a speed of 4 ℃/min under the protection of argon in a tubular furnace, calcining for 4 hours at a high temperature, and cooling to room temperature at a speed of 4 ℃/min to obtain the 3-D open-framework porous electrocatalyst.
And carrying out morphology characterization on the prepared catalyst, and analyzing the structure. FIG. 1 is a scanning electron microscope image and an elemental analysis image of a 3-D open-framework porous electrocatalyst. As shown in FIG. 1, the electrocatalyst particles have a spherical morphology around 100nm, and a large number of particles agglomerate to form a porous structure, which may be CO 2 Provides an ultra-high active area. The elemental analysis map of fig. 1 shows that only Mn, Y, N, C elements are present in the catalyst and are uniformly distributed, indicating that the phase of the synthesized catalyst is uniform.
And carrying out X-ray crystal diffraction test on the prepared 3-D open-framework porous electrocatalyst, and analyzing the crystal form of the catalyst. FIG. 2 is an X-ray crystal diffraction pattern of a 3-D open-framework porous electrocatalyst. As shown in FIG. 2, which is an X-ray crystal diffraction diagram of a 3-D open-framework porous electrocatalyst, the catalyst is characterized in that Mn-Y is mainly dispersed in atomic scale and has an amorphous peak of C.
Example 2: prepared 3-D open-framework porous electrocatalyst
A method for preparing a 3-D open-framework porous electrocatalyst, comprising the steps of:
s1, 12.6mg of manganese chloride, 97.6mg of yttrium chloride and 122.1mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are added into 12mL of ultrapure water, ultrasonic treatment is carried out for 15min until complete dissolution, and mixing and stirring are carried out, thus obtaining a catalyst precursor synthesis stock solution;
s2, transferring the catalyst precursor synthesized stock solution obtained in the step S1 into a 30mL tetrafluoroethylene reaction kettle, heating at 170 ℃ for 68 hours, and cooling the reaction kettle to room temperature at 10 ℃/h after heating is finished to obtain a solid-liquid mixture;
s3, centrifuging the solid-liquid mixture obtained in the step S2 at 12000rpm for 1min, washing the centrifugally separated solid with ultrapure water for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor of the catalyst;
s4, heating the precursor of the catalyst 10mg obtained in the step S3 and 55mg of carbon black to 850 ℃ at a speed of 4 ℃/min under the protection of argon in a tubular furnace, calcining for 3 hours at a high temperature, and cooling to room temperature at a speed of 4 ℃/min to obtain the 3-D open-framework porous electrocatalyst.
Example 3: prepared 3-D open-framework porous electrocatalyst
A method for preparing a 3-D open-framework porous electrocatalyst, comprising the steps of:
s1, 12.6mg of manganese chloride, 97.6mg of yttrium chloride and 122.1mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are added into 9mL of ultrapure water, ultrasonic treatment is carried out for 18min until complete dissolution, and mixing and stirring are carried out, thus obtaining a catalyst precursor synthesis stock solution;
s2, transferring the catalyst precursor synthesized stock solution obtained in the step S1 into a 28mL tetrafluoroethylene reaction kettle, heating at 180 ℃ for 80 hours, and cooling the reaction kettle to room temperature at 10 ℃/h after heating is finished to obtain a solid-liquid mixture;
s3, centrifuging the solid-liquid mixture obtained in the step S2 at 10000rpm for 3min, washing the centrifugally separated solid with ultrapure water for 3 times, and drying in a vacuum drying oven at 50 ℃ to obtain a precursor of the catalyst;
s4, heating the precursor of the catalyst 10mg obtained in the step S3 and 55mg of carbon black to 900 ℃ at a speed of 4 ℃/min under the protection of argon in a tubular furnace, calcining for 3 hours at a high temperature, and cooling to room temperature at a speed of 4 ℃/min to obtain the 3-D open-framework porous electrocatalyst.
Test example 1: electrocatalytic reduction carbon dioxide test
4g of the electrocatalyst obtained in example 1 was completely dispersed in 4mL of ethanol, 40. Mu.L of a 5% nafion D520 solution was added to give a brown transparent dispersion, and 1mL of the electrocatalyst suspension was sprayed onto a 1X 1cm area 2 And air-drying the commercial conductive carbon paper to prepare the working electrode for electrocatalytically reducing carbon dioxide.
In order to test the catalytic performance, a linear sweep voltammetry test is carried out on a working electrode, a high-purity graphite rod is used as a counter electrode, ag/AgCl is used as a reference electrode, and 0.1M KHCO is used 3 The solution is electrolyte, in an H-type electrolytic cell, ar and CO are respectively adopted 2 The test was performed under the conditions. As shown in FIG. 3, at the same potential, the working electrode is at CO 2 The current density under the flowing in is obviously higher than that under the flowing in Ar, which proves that the electrocatalyst has good electrocatalytic CO 2 Performance of reduction.
And assembling the working electrode in an H-type electrolytic cell to perform carbon dioxide electroreduction tests under different potentials. The test uses a high-purity graphite rod as a counter electrode, ag/AgCl as a reference electrode and 0.1M KHCO 3 The solution is an electrolyte. Introducing 30minCO before electrolysis 2 By bringing the electrolyte CO into contact with 2 Saturation, then electrocatalytic performance testing at-0.70V, -0.75V, -0.80V, -0.85V, -0.90V, -0.95V, -1.00V, -1.05V,1.10V (each relative to the reversible hydrogen electrode) potentials gave a faraday efficiency of 74.8%,88.6%,92.3%,96.6%,91.7%,88.3%,86.2%,82.7%,79.5% CO, respectively, production at each potentialThe distribution is shown in FIG. 4, and it can be seen that the Faraday efficiency of CO reaches a maximum of 96.6% at-0.85V.
Test example 2: stability test of electrocatalytic reduction carbon dioxide
4g of the electrocatalyst obtained in example 1 was completely dispersed in 4mL of ethanol, 40. Mu.L of a 5% nafion D520 solution was added to give a brown transparent dispersion, and 1mL of the electrocatalyst suspension was sprayed onto a 1X 1cm area 2 And air-drying the commercial conductive carbon paper to prepare the working electrode for electrocatalytically reducing carbon dioxide.
The working electrode is assembled in an H-type electrolytic cell for carbon dioxide electroreduction stability test. The test uses a high-purity graphite rod as a counter electrode, ag/AgCl as a reference electrode and 0.1M KHCO 3 The solution is an electrolyte. CO is introduced for 30min before electrolysis 2 By bringing the electrolyte CO into contact with 2 Saturation and then the catalyst electrocatalytic stability performance test was carried out for a time of 12000s at a potential of-0.85V. As shown in the data of FIG. 5, the electrocatalyst was operated at a current of 18mA with no significant decay in 12000s current density.
While the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and other various modifications and variations may be made within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
1. A method for preparing a 3-D open-framework porous electrocatalyst, which is characterized by comprising the following steps:
s1, dissolving manganese chloride, yttrium chloride and 2,2 '-bipyridine-5, 5' -dicarboxylic acid in ultrapure water, mixing and stirring to obtain a catalyst precursor synthesis stock solution;
s2, transferring the catalyst precursor synthesized stock solution obtained in the step S1 into a tetrafluoroethylene reaction kettle for heating, and cooling the reaction kettle to room temperature at 10 ℃/h after heating is finished to obtain a solid-liquid mixture;
s3, centrifuging the solid-liquid mixture obtained in the step S2, cleaning the centrifugally separated solid with ultrapure water for 3-5 times, and drying to obtain a precursor of the catalyst;
s4, heating the precursor of the catalyst obtained in the step S3 and carbon black to 700-900 ℃ at a speed of 4 ℃/min under the protection of argon in a tube furnace, calcining at a high temperature for 3-5 hours, and cooling to room temperature at a speed of 4 ℃/min to obtain a 3-D open-framework porous electrocatalyst;
in S1, the mass ratio of the manganese chloride to the yttrium chloride to the 2,2 '-bipyridine-5, 5' -dicarboxylic acid to the ultrapure water is (0.4-2): (8-11): (10-14): (800-1200);
and S2, heating, namely placing the reaction kettle in a baking oven at 160-180 ℃ and heating for 60-80 hours.
2. The method according to claim 1, wherein in S1, the dissolution is performed using ultrasound for 10 to 20 minutes.
3. The method according to claim 1, wherein in S3, the centrifugal speed is 8000-12000rpm for 1-3min.
4. The method according to claim 1, wherein in S3, the drying is performed by heating in a vacuum oven at 50-60 ℃ for 1-2 hours.
5. The preparation method according to claim 1, wherein in S4, the mass ratio of the precursor of the catalyst to the carbon black is 1:4-6.
6. A 3-D open-framework porous electrocatalyst produced by the production process according to any one of claims 1 to 5.
7. Use of a 3-D open-framework porous electrocatalyst prepared by the method of any one of claims 1 to 5 for electrocatalytic reduction of carbon dioxide.
8. The use according to claim 7, characterized in that commercial conductive carbon paper loaded with 3-D open-framework porous electrocatalyst is used as working electrode, high purity graphite rod is used as counter electrode, ag/AgCl is used as reference electrode, and electrolyte is KHCO of 0.1M 3 Introducing CO into H-type electrolytic cell at constant voltage of-1.47V 2 And (5) carrying out electrolysis to obtain CO.
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CN113186565A (en) * | 2021-04-14 | 2021-07-30 | 天津大学 | Preparation method of novel nitrogen-doped carbon material for electrocatalytic reduction of carbon dioxide |
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