CN113663716B - Indium oxide loaded metal monatomic catalyst and application thereof - Google Patents

Indium oxide loaded metal monatomic catalyst and application thereof Download PDF

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CN113663716B
CN113663716B CN202111142298.6A CN202111142298A CN113663716B CN 113663716 B CN113663716 B CN 113663716B CN 202111142298 A CN202111142298 A CN 202111142298A CN 113663716 B CN113663716 B CN 113663716B
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indium oxide
nitrogen
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CN113663716A (en
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管国锋
丁靖
张伟
吴俊�
李鑫
万辉
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Nanjing Tech University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract

The invention relates to an indium oxide loaded metal monatomic catalyst and application thereof. The catalyst is prepared by the following steps: (1) adding the mixture of indium salt and amino phthalic acid into a solvent for dissolving, uniformly stirring, reacting, filtering, washing and drying to obtain MIL-68(In) -NH2(ii) a (2) Dissolving acetylacetone metallorganic In solvent, and adding MIL-68(In) -NH2Reacting under the protection of nitrogen; (3) and filtering, washing and vacuum drying a product obtained after the reaction, and carbonizing the product in a tubular furnace under the protection of inert gas to obtain the indium oxide supported metal type monatomic catalyst. The indium oxide supported metal monatomic catalyst provided by the invention can be used for catalyzing co-conversion of methane and carbon dioxide to directly prepare acetic acid, and has good catalytic activity and selectivity under a low-pressure condition.

Description

Indium oxide loaded metal monatomic catalyst and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to preparation and application of an indium oxide loaded metal monatomic catalyst.
Background
Acetic acid is an important product of the food industry and also an important intermediate for many commercial chemicals, such as the production of acetic anhydride, vinyl acetate, alkyl acetates and as solvents for the synthesis of terephthalic acid. Acetic acid is one of important organic chemical raw materials, is widely used in industries such as synthetic fibers, coatings, pesticides, medicines, food additives, dyeing and weaving and the like, and is an important component of national economy. In China, acetic acid production begins in the 60 th of the 20 th century, ethanol oxidation is mostly adopted for preparing acetic acid in the early stage, and then a methanol carbonylation method, a low-carbon alkane liquid-phase oxidation method, an acetaldehyde oxidation method and an ethylene oxidation method are mainly adopted. Among them, the methanol carbonylation method is favored because of high conversion rate and selectivity, wide sources of carbon monoxide and methanol as raw materials, low price and low production cost. However, this method generally requires a noble metal as a catalyst and requires separation of the catalyst and water in addition to the use of a halide, resulting in an increase in process cost (Catal. Sci. technol.,2017,7, 4818-.
CH4And CO2Direct conversion to acetic acid is a green reaction with 100% atomic utilization, which can greatly reduce the use of noble metal catalysts, reduce the process cost, and reduce the emission of greenhouse gases (appl. cat. Based on the above, Abdelrahmann M. Rabie developed a new method for directly synthesizing acetic acid, which jointly activates methane and carbon dioxide by one-step method, and the Cu-K-ZSM-5 catalyst prepared by the method can stabilize the generation rate of acetic acid at 395 mu mol g in the reaction for 10 hourscat -1·h-1And the selectivity performance is as high as 95%. The Huangwei research group of Shanxi coal chemical institute of Taiyuan university has long dedicated to the research of C1 chemistry, and the developed methane-carbon dioxide two-step method successfully bypasses thermodynamic limitation and successfully prepares acetic acid, but the selectivity of the acetic acid is relatively low. In patent publication No. CN111675609A (a low temperature plasma and a supported copper-based catalyst synergistically converting CH in one step4And CO2Method for producing acetic acid) uses low temperature plasma technology to catalyze and produce acetic acid, but the reaction selectivity is low; in patent publication No. CN202011230364.0 (a catalyst for methane carbon dioxide reforming to synthesis gas and a method for preparing the same), the synthesis gas is the final product, and acetic acid is not directly prepared in one step. Therefore, the process for preparing acetic acid is highly efficient and highThe design and development of selective catalyst have become the key to catalyze the co-conversion of methane and carbon dioxide to directly prepare acetic acid.
Disclosure of Invention
The invention aims to improve the defects of the prior art and provides an indium oxide supported metal monatomic catalyst, and the invention also aims to provide the application of the catalyst to the catalysis of CH4With CO2Directly preparing acetic acid.
In order to achieve the purpose, the technical scheme of the invention is as follows: an indium oxide supported metal monatomic catalyst is prepared by the following method, and the method comprises the following specific steps:
(1) adding the mixture of indium salt and aminobenzoic acid into N, N-Dimethylformamide (DMF) solution for dissolving, reacting after uniformly stirring, filtering, washing and drying to obtain MIL-68(In) -NH2；
(2) Mixing acetylacetone metallorganic with MIL-68(In) -NH2Respectively adding the mixture into a solvent for dissolving, mixing, and reacting under the protection of nitrogen;
(3) and filtering, washing and vacuum drying the product obtained after the reaction, and carbonizing the product in a tubular furnace for 1-5 hours under a protective atmosphere to obtain the indium oxide loaded metal monatomic catalyst. The obtained catalyst is marked as SAs-M-In2O3/CN。
Preferably, the indium salt in the step (1) is one of indium nitrate, indium sulfate, indium chloride and indium acetate; the amino phthalic acid is one of 2-amino terephthalic acid, 3-amino phthalic acid or 4-amino phthalic acid.
Preferably, the mass ratio of the indium salt and the aminobenzoic acid to the added DMF solution in the step (1) is (1-5) to (1) (60-80); the reaction temperature is 80-140 ℃, and the reaction time is 1-6 h.
Preferably, In the step (2), acetylacetone metallorganic compound, MIL-68(In) -NH2The mass ratio of the solvent to the solvent is 1 (1-10) to 10-40; the reaction temperature is 25-70 ℃, and the reaction time is 4-12 h; .
Preferably, the acetylacetone metallorganic in step (2) is one of iron acetylacetonate, cobalt acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zinc acetylacetonate, or nickel acetylacetonate; the solvent is one of methanol, N-dimethylformamide, toluene or chloroform.
Preferably, the carbonization temperature in the step (3) is 700-900 ℃; the heating rate is 2-10 ℃ per minute-1(ii) a Flow rate of 10-60 mL/min-1(ii) a The protective atmosphere is one of nitrogen, argon or helium. M is one of Fe, Co, Mn, Cu, Zn or Ni.
The invention also provides application of the indium oxide loaded metal monatomic catalyst in direct preparation of acetic acid from methane and carbon dioxide. The method comprises the following specific steps: 1) mixing a catalyst and quartz sand, and adding the mixture into a stainless steel micro flowing fixed bed reactor with the inner diameter of 6-10 mm; 2) nitrogen purging, heating, hydrogen reduction and heating to reaction temperature; or purging with nitrogen and heating to reaction temperature; 3) then introducing a certain flow rate of methane and carbon dioxide for reaction.
The mass ratio of the catalyst to the quartz sand is preferably 1 (100-150); blowing with nitrogen at 2-10 deg.C/min-1Heating to 300-450 deg.c; the reduction flow of hydrogen is 10-60 mL/min-1The reduction time is 3-12 h; at 2-10 ℃ per minute-1Heating to the reaction temperature of 400-600 ℃; the volume flow ratio of methane to carbon dioxide is 1 (1-3); the reaction pressure is 1-10 atm.
Has the beneficial effects that:
the indium oxide supported metal monatomic catalyst provided by the invention can be used for catalyzing co-conversion of methane and carbon dioxide to directly prepare acetic acid, and has good catalytic activity and selectivity under a low-pressure condition.
Detailed Description
The present invention is described in more detail below with reference to examples. These examples are only illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
Step 1, adding a mixture of indium nitrate and 3-aminophthalic acid in a mass ratio of 5:1:80 into a N, N-Dimethylformamide (DMF) solution, and stirringUniformly reacting at 80 ℃ for 6h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing ferric acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:1:402Respectively adding the mixture into methanol for dissolving, mixing and reacting for 12 hours at 25 ℃ under the protection of nitrogen;
and 3, filtering, washing and vacuum drying a product obtained after the reaction, and carbonizing the product for 4 hours in a tubular furnace under the protection of argon, wherein the carbonization temperature is 700 ℃, and the heating rate is 2 ℃ per minute-1Flow rate of 10 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst, wherein the obtained catalyst is marked as SAs-Fe-In2O3/CN。
Example 2
Step 1, adding a mixture of indium chloride and 2-amino terephthalic acid In a mass ratio of 1:1:60 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 110 ℃ for 1h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing cobalt acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:10:102Respectively adding the mixture into toluene and methanol for dissolving, mixing and reacting for 4 hours at 70 ℃ under the protection of nitrogen;
step 3, filtering, washing and vacuum drying the product obtained after the reaction, carbonizing the product for 2 hours in a tubular furnace under the protection of argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 10 ℃ per minute-1Flow rate of 30 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst for directly preparing acetic acid by Co-converting methane and carbon dioxide, wherein the obtained catalyst is marked as SAs-Co-In2O3/CN。
Example 3
Step 1, adding a mixture of indium acetate and 4-aminophthalic acid In a mass ratio of 3:1:70 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 130 ℃ for 4h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing copper acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:3:202Dissolving in DMF and methanol respectively, and mixingMixing and reacting for 10h at 70 ℃ under the protection of nitrogen;
step 3, filtering, washing and vacuum drying the product obtained after the reaction, carbonizing the product for 1h in a tubular furnace under the protection of nitrogen, wherein the carbonizing temperature is 900 ℃, and the heating rate is 5 ℃ min-1Flow rate of 20 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst for directly preparing acetic acid by co-converting methane and carbon dioxide, wherein the obtained catalyst is marked as SAs-Cu-In2O3/CN。
Example 4
Step 1, adding a mixture of indium nitrate and 2-amino terephthalic acid In a mass ratio of 4:1:60 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 140 ℃ for 3h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing manganese acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:4:102Respectively adding the mixture into chloroform and DMF for dissolving, mixing and reacting for 8 hours at 60 ℃ under the protection of nitrogen;
step 3, filtering, washing and vacuum drying the product obtained after the reaction, carbonizing the product for 5 hours in a tubular furnace under the protection of helium, wherein the carbonization temperature is 750 ℃, and the heating rate is 3 ℃ per minute-1Flow rate of 30 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst, wherein the obtained catalyst is marked as SAs-Mn-In2O3/CN。
Example 5
Step 1, adding a mixture of indium chloride and 4-aminophthalic acid In a mass ratio of 2:1:60 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 100 ℃ for 5 hours, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing zinc acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:5:202Respectively adding the mixture into chloroform and methanol for dissolving, mixing and reacting for 9 hours at 40 ℃ under the protection of nitrogen;
step 3, filtering, washing and vacuum drying the product obtained after the reaction, carbonizing the product for 2 hours in a tubular furnace under the protection of nitrogen, wherein the carbonization temperature is 900 ℃, and the heating rate is 5 ℃ per minute-1Flow rate 50 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst, wherein the obtained catalyst is marked as SAs-Zn-In2O3/CN。
Example 6
Step 1, adding a mixture of indium acetate and 2-amino terephthalic acid In a mass ratio of 1:1:80 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 100 ℃ for 2h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, nickel acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:9:302Respectively adding the mixture into chloroform and methanol for dissolving, mixing and reacting for 12 hours at 70 ℃ under the protection of nitrogen;
step 3, filtering, washing and vacuum drying the product obtained after the reaction, and carbonizing the product for 3 hours in a tubular furnace under the protection of argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 3 ℃ per minute-1Flow rate 60 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst, wherein the obtained catalyst is marked as SAs-Ni-In2O3/CN。
Example 7
Step 1, adding a mixture of indium nitrate and 3-aminophthalic acid In a mass ratio of 3:1:60 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 140 ℃ for 3h, filtering, washing, and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing copper acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:6:402Respectively adding the mixture into toluene and N, N-dimethylformamide for dissolving, then mixing and reacting for 8 hours at 60 ℃ under the protection of nitrogen;
and 3, filtering, washing and vacuum drying a product obtained after the reaction, carbonizing the product for 2 hours in a tubular furnace under the protection of argon, wherein the carbonization temperature is 750 ℃, and the heating rate is 2 ℃ per minute-1Flow rate of 40 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst for directly preparing acetic acid by co-converting methane and carbon dioxide, wherein the obtained catalyst is marked as SAs-Cu-In2O3/CN。
Example 8
Step 1, adding a mixture of indium chloride and 4-aminophthalic acid In a mass ratio of 4:1:70 into a N, N-Dimethylformamide (DMF) solution, uniformly stirring, reacting at 120 ℃ for 6h, filtering, washing and drying In vacuum to obtain MIL-68(In) -NH2；
Step 2, mixing ferric acetylacetonate and MIL-68(In) -NH In a mass ratio of 1:6:202Respectively adding the mixture into toluene and methanol for dissolving, mixing and reacting for 10 hours at 50 ℃ under the protection of nitrogen;
and 3, filtering, washing and vacuum drying a product obtained after the reaction, and carbonizing the product for 3 hours in a tubular furnace under the protection of argon at the carbonization temperature of 850 ℃ and the heating rate of 3 ℃ per minute-1Flow rate 50 mL/min-1. Obtaining the indium oxide loaded metal monatomic catalyst, wherein the obtained catalyst is marked as SAs-Fe-In2O3/CN。
Catalyzing methane and carbon dioxide to carry out cotransformation to synthesize acetic acid by using a metal monatomic catalyst:
application example 1
SAs-Fe-In with the mass ratio of 1:1002O3the/CN catalyst (prepared in example 1) was mixed with quartz sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 6mm, purged with nitrogen at 5 ℃ min-1The temperature is raised to 500 ℃, reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:1, and the reaction pressure is 10 atm. The gas phase product was analyzed on-line by gas chromatography with a selectivity of 96.02% and an acetic acid formation rate of 254. mu. mol. gcat -1·h-1。
Application example 2
SAs-Co-In with the mass ratio of 1:1502O3the/CN catalyst (prepared in example 2) was mixed with quartz sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 8mm, purged with nitrogen at 10 ℃ min-1The temperature is raised to 400 ℃, reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:2, and the reaction pressure is 5 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 98.30%, and the rate of formation of acetic acid was 213. mu. mol. gcat -1·h-1。
Application example 3
Mixing SAs-Cu-In with the mass ratio of 1:1102O3the/CN catalyst (prepared in example 3) was mixed with quartz sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 10mm, purged with nitrogen at 8 ℃ min-1The temperature was raised to 300 ℃ at a rate of 10 mL. min, and hydrogen was switched-1The flow rate of (2) is reduced for 3h, nitrogen purging is switched, and the temperature is 5 ℃ min-1The temperature is raised to 550 ℃, reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:1, and the reaction pressure is 6 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 99.05%, and the rate of formation of acetic acid was 249. mu. mol. gcat -1·h-1。
Application example 4
SAs-Mn-In with the mass ratio of 1:1202O3the/CN catalyst (prepared in example 4) was mixed with silica sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 7mm, purged with nitrogen at 9 ℃ min-1At the rate of 600 ℃, introducing reaction gas, wherein the volume flow ratio of methane to carbon dioxide is 1:3, and the reaction pressure is 4 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 96.06%, and the rate of formation of acetic acid was 202. mu. mol. gcat -1·h-1。
Application example 5
SAs-Zn-In with the mass ratio of 1:1302O3the/CN catalyst (prepared in example 5) was mixed with quartz sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 9mm, purged with nitrogen at 5 ℃ min-1The temperature is raised to 425 ℃ at the rate of (2), reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:1, and the reaction pressure is 7 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 97.20%, and the rate of formation of acetic acid was 376. mu. mol. gcat -1·h-1。
Application example 6
Mixing SAs-Ni-In with the mass ratio of 1:1402O3the/CN catalyst (prepared in example 6) was mixed with silica sand and fed into a stainless steel micro-flow fixed bed reactor having an inner diameter of 10mm, purged with nitrogen at 10 ℃ min-1Heating to 450 deg.C, cuttingChanging hydrogen gas at 30 mL/min-1Reducing for 2 hours, switching nitrogen purging, introducing reaction gas, wherein the volume flow ratio of methane to carbon dioxide is 1:2, and the reaction pressure is 3 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 98.06%, and the rate of formation of acetic acid was 198. mu. mol. gcat -1·h-1。
Application example 7
SAs-Cu-In with the mass ratio of 1:1502O3the/CN catalyst (prepared in example 7) was mixed with silica sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 6mm, purged with nitrogen at 10 ℃ min-1The temperature was raised to 300 ℃ at a rate of 60 mL. min, and hydrogen was switched-1The flow rate of (2) is reduced for 3h, nitrogen purging is switched, and the temperature is 10 ℃ min-1The temperature is raised to 500 ℃, reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:1, and the reaction pressure is 8 atm. The gas phase product was analyzed by gas chromatography on-line, the selectivity was 96.54%, and the rate of formation of acetic acid was 328. mu. mol. gcat -1·h-1。
Application example 8
SAs-Fe-In with the mass ratio of 1:1302O3the/CN catalyst (prepared in example 8) was mixed with quartz sand and charged into a stainless steel micro-flow fixed bed reactor having an inner diameter of 6mm, purged with nitrogen at 8 ℃ min-1The temperature is raised to 600 ℃, reaction gas is introduced, the volume flow ratio of methane to carbon dioxide is 1:3, and the reaction pressure is 1 atm. The gas phase product was analyzed on-line by gas chromatography, the selectivity was 94.80%, and the rate of formation of acetic acid was 301. mu. mol. gcat -1·h-1。
TABLE 1 catalysts SAs-M-In2O3Results of the/CN Performance test
Figure BDA0003284206470000091

Claims (6)

1. An indium oxide supported metal monatomic catalyst is prepared by the following method, and the method comprises the following specific steps:
(1) adding the mixture of indium salt and aminobenzoic acid into N, N-dimethylformamide DMF solution for dissolving, uniformly stirring, reacting, filtering, washing and drying to obtain MIL-68(In) -NH2(ii) a Wherein the mass ratio of the indium salt to the amino phthalic acid to the added DMF solution is (1-5) to (1) (60-80); the reaction temperature is 80-140 ℃, and the reaction time is 1-6 h;
(2) mixing acetylacetone metallorganic with MIL-68(In) -NH2Respectively adding the mixture into a solvent for dissolving, mixing, and reacting under the protection of nitrogen; wherein acetylacetone metallorganics, MIL-68(In) -NH2The mass ratio of the solvent to the solvent is 1 (1-10) to 10-40; the reaction temperature is 25-70 ℃, and the reaction time is 4-12 h;
(3) filtering, washing and vacuum drying a product obtained after the reaction, and carbonizing the product in a tubular furnace for 1-5 hours under a protective atmosphere to obtain an indium oxide loaded metal monatomic catalyst; wherein the carbonization temperature is 700-900 ℃; the temperature rise rate is 2-10 ℃ for min-1(ii) a Flow rate of 10-60 mL.min-1(ii) a The protective atmosphere is one of nitrogen, argon or helium.
2. The indium oxide-supported metal monatin type catalyst according to claim 1, wherein: the indium salt in the step (1) is one of indium nitrate, indium sulfate, indium chloride or indium acetate; the amino phthalic acid is one of 2-amino terephthalic acid, 3-amino phthalic acid or 4-amino phthalic acid.
3. The indium oxide-supported metal monatin type catalyst according to claim 1, wherein: the acetylacetone metal organic matter in the step (2) is one of iron acetylacetonate, cobalt acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zinc acetylacetonate or nickel acetylacetonate; the solvent is one of methanol, N-dimethylformamide, toluene or chloroform.
4. Use of the indium oxide supported metal monatomic catalyst according to claim 1 in the direct production of acetic acid from methane and carbon dioxide.
5. The application of claim 4, which comprises the following specific steps: 1) mixing a catalyst and quartz sand, and adding the mixture into a stainless steel micro flowing fixed bed reactor with the inner diameter of 6-10 mm; 2) nitrogen purging, heating, hydrogen reduction and heating to reaction temperature; or purging with nitrogen and heating to reaction temperature; 3) then introducing a certain flow rate of methane and carbon dioxide for reaction.
6. Use according to claim 4, characterized in that: the mass ratio of the catalyst to the quartz sand is 1 (100-150); nitrogen purging at 2-10 ℃ for min-1Heating to 300-450 deg.c; the reduction flow of hydrogen is 10-60 mL.min-1The reduction time is 3-12 h; at 2-10 ℃ for min-1Heating to the reaction temperature of 400-600 ℃; the volume flow ratio of methane to carbon dioxide is 1 (1-3); the reaction pressure is 1-10 atm.
CN202111142298.6A 2021-09-28 2021-09-28 Indium oxide loaded metal monatomic catalyst and application thereof Active CN113663716B (en)

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