WO2016167698A1 - Catalysed baeyer-villiger oxidation of cyclic ketones - Google Patents
Catalysed baeyer-villiger oxidation of cyclic ketones Download PDFInfo
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- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
Definitions
- the present invention refers to a process for Baeyer-Villiger oxidation of a cyclic ketone yielding a corresponding lactone by oxidation of said cyclic ketone using hydrogen peroxide as oxidant.
- Said oxidation is performed in presence of a catalytically active amount of at least one catalyst comprising Sn, Se and/or Zn in an amount of 0.1-1 mmol/g, calculated as elemental substance, on a carrier material.
- the Baeyer-Villiger oxidation is an organic reaction wherein an ester is formed from a linear ketone or a lactone from a cyclic ketone. Typically peroxyacids and less frequently peroxides, as these are less reactive than peroxyacids, are used as oxidants.
- the first step in such a Baeyer-Villiger lactone synthesis is the generation of the peroxyacid used to oxidise the cyclic ketone. This reaction step can be illustrated by below reaction scheme wherein a peroxyacid is formed from a carboxylic acid and hydrogen peroxide
- the peroxyacid reacts with the cyclic ketone yielding a lactone and a carboxylic acid according to below reaction scheme wherein cyclohexanone is reacted with a peroxyacid
- the peroxyacid attacks the carbon of the carbonyl group forming a so called Criegee intermediate.
- a concerted mechanism one of the substituents on the ketone migrates to the oxygen of the peroxy group while a carboxylic acid leaves. Finally, deprotonation of the oxygen of the carbonyl group produces the lactone.
- the Baeyer-Villiger oxidation of cyclic ketones using peroxyacids as oxidants is typically, due to the corrosivity of peroxyacids, performed in a series of expensive glass, or glass lined, and/or tantalum reactors and in absence of any catalyst.
- the selectivity toward the cyclic ketones is, using peroxyacids as oxidants, typically around 90%.
- the carrier material is preferably selected from for instance a zeolite, such as a beta zeolite, a ceramic material, such as A1 2 0 3 , or a mesocellular foam.
- Sn, Se and/or Zn is/are, in embodiments of the present invention, present as a catalytically active organic or inorganic compound and/or as elemental substance and present in said oxidation at a molar ratio Sn, Se and/or Zn, calculated as elemental substance, to reactants, cyclic ketone and hydrogen peroxide, of between 0.001 : 1 and 0.05: 1, such as between 0.003: 1 and 0.3: 1 or between 0.005: 1 and 0.01 : 1.
- the present process is furthermore optionally performed in presence of at least one azeotropic solvent, such as a non-polar solvent and can be performed as a continuos, a semi-continuos or a batch process.
- Said catalyst can be employed as a powder, a spray-powder, a moulding, such as rings, rods, pellets and similar, or any other form known in the art and used in batch mode, semi-continuos mode or continuous mode, such as in a fixed-bed catalyst mode.
- Said cyclic ketone is in preferred embodiments of the present invention a saturated lactone, cyclohexanone yielding ⁇ -caprolactone is especially preferred, and said process is preferably performed at a ratio hydrogen peroxide to said cyclic ketone of between 1 : 1 and 1 :3.5.
- Said optional azeotropic solvent is, in likewise preferred embodiments, an acetonitrile, a propionitrile, a 1 ,2-dichloroalkane, chloroform, a 1,4-dioxane, a dialkylether, an alkyl acetate and/or an alkyl or dialkyl carbonate.
- the most preferred solvents include, but is not limited to, 1,4-dioxane and/or methyl tert.butyl ether.
- the present process can of course also be performed using a catalyst selected from for instance Mn, Cr, Rh, Ru, Ni, Ca, Na, K, Cu, Ag, Cs, Fe, Ir, Pd, Pt, Al or Ti, as organic or inorganic compound and/or as elemental metal, and/or any combination whereof or wherewith as sole catalyst or as co-catalyst.
- Said metals or metal compounds, as well as Sn, Se and Zn can of course also be loaded on any other zeolite, such as a MWW zeolite, any ceramic material, any mesocellular foams or on kiselguhr, carbon, asbestos, chalk or any other carrier known in the art.
- N-heterocyclic carbenes can, furthermore, be used as co-catalysts.
- Examples 1-4 refer to embodiments of the Baeyer-Villiger oxidation according to the present invention and Figure 1 schematically shows a distillation set up as used in said Examples.
- Hydrogen peroxide (37%) and cyclohexanone (99.9%) were in a ratio 1 :2 fed to a steel tube reactor and reacted in presence of a Zn beta zeolite catalyst, having a Zn content of 0.32 mmol/g, and 1,4-dioxane as azeotropic solvent, yielding ⁇ -caprolactone at a selectivity of 95.2% toward cyclohexanone.
- Used amount of catalyst was 0.5 mol% calculated as elemental metal and the reaction temperature was 60°C.
- Example 1 was repeated with the difference that a Sn beta zeolite, having a Sn content of 0.40 mmol/g, was used instead of the Zn catalyst and methyl tert.butyl ether was used as azeotropic solvent instead of 1,4-dioxane.
- the selectivity toward cyclohexanone was 94.9%. Recovery as in Example 1.
- Example 3
- Example 1 was repeated with the difference that a Se catalyst, having a Se content of 0.38 mmol/g, on a mesocellular foam was used instead of the Zn catalyst.
- the selectivity toward cyclohexanone was 94.7%. Recovery as in Example 1.
- Example 1 was repeated with the difference that a Sn catalyst, having a Sn content of 0.52 mmol/g, on A1 2 0 3 was used instead of the Zn catalyst.
- the selectivity toward cyclohexanone was 92.5%. Recovery as in Example 1.
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Abstract
Disclosed is a catalysed Baeyer-Villiger oxidation of cyclic ketones yielding corresponding lactones. Hydrogen peroxide is used as oxidant and said oxidation is catalysed by a catalytically active amount of at least one catalyst comprising Sn, Se and/or Zn loaded in an amount of 0.1-1 mmol/g, calculated as elemental substance, on a carrier material. An azeotropic solvent, such as a non-polar solvent is optionally used.
Description
CATALYSED BAEYER-VILLIGER OXIDATION OF CYCLIC KETONES
The present invention refers to a process for Baeyer-Villiger oxidation of a cyclic ketone yielding a corresponding lactone by oxidation of said cyclic ketone using hydrogen peroxide as oxidant. Said oxidation is performed in presence of a catalytically active amount of at least one catalyst comprising Sn, Se and/or Zn in an amount of 0.1-1 mmol/g, calculated as elemental substance, on a carrier material.
The Baeyer-Villiger oxidation is an organic reaction wherein an ester is formed from a linear ketone or a lactone from a cyclic ketone. Typically peroxyacids and less frequently peroxides, as these are less reactive than peroxyacids, are used as oxidants. The first step in such a Baeyer-Villiger lactone synthesis is the generation of the peroxyacid used to oxidise the cyclic ketone. This reaction step can be illustrated by below reaction scheme wherein a peroxyacid is formed from a carboxylic acid and hydrogen peroxide
After protonation under acidic conditions the carboxylic acid molecule is attacked by the hydrogen peroxide and generates after expulsion of water a peroxyacid.
In a preceding step, the peroxyacid reacts with the cyclic ketone yielding a lactone and a carboxylic acid according to below reaction scheme wherein cyclohexanone is reacted with a peroxyacid
The peroxyacid attacks the carbon of the carbonyl group forming a so called Criegee intermediate. Through a concerted mechanism, one of the substituents on the ketone migrates to the oxygen of the peroxy group while a carboxylic acid leaves. Finally, deprotonation of the oxygen of the carbonyl group produces the lactone.
The Baeyer-Villiger oxidation of cyclic ketones using peroxyacids as oxidants is typically, due to the corrosivity of peroxyacids, performed in a series of expensive glass, or glass lined,
and/or tantalum reactors and in absence of any catalyst. The selectivity toward the cyclic ketones is, using peroxyacids as oxidants, typically around 90%.
There is an increasing interest and desire in making the Baeyer-Villiger oxidation work with hydrogen peroxide as oxidant. The use of hydrogen peroxide as oxidant implies advantages, such as being cheap, having a high content of active oxygen and being environmentally friendlier since the formed waste product is water only. However, hydrogen peroxide requires a catalyst in order to be used as oxidant in a Baeyer-Villiger oxidation.
The first reported instance of an asymmetric Baeyer-Villiger oxidation on a prochiral ketone used 02 as oxidant and a copper catalyst (Craig Seymour, "The Asymmetric Baeyer-Villiger Oxidation, Traditional Synthetic Methods Versus Enzymes", Group Meeting Presentation 16 July 2013, online version). Other catalysts followed such as platinum and aluminium catalysts.
The use of benzene seleninic acids, such as 3,5-fos(trifluoromefhyl)benzene selenic acid formed in situ from bw[3,5-6w(trifluoromethyl)phenyl] diselenide, as catalysts with hydrogen peroxide has been reported - G-J. ten Brink et al, "Selenium-Catalysed Oxidation with Aqueous Hydrogen Peroxide. 2. Baeyer-Villiger Reaction in Homogeneous Solution", J. Org. Chem. 2001, 66, 2429-2433.
Avolino Corma et al report in "Sn-zeolite beta as a heterogeneous chemoselctive catalyst for Baeyer-Villiger oxidations" Nature vol. 412, 26 July 2001, the use of Sn incorporated into a beta zeolite (typically zeolite has a formula of X2Al2Si3Oio · 2 H20 wherein X typically is K, Na, Ca or Mg) framework as catalyst in Baeyer-Villiger oxidations of saturated and unsaturated ketones by hydrogen peroxide. However, only the exceptionally large amount of 1.6 weight-% of Sn, roughly corresponding to 1.8-2.2 mmol/g depending on the zeolite framework structure and cation, of Sn calculated as elemental metal on zeolite, was tested with a capro lactone yield of only 52% from cyclohexanone.
Chunxia Chen et al "The Catalytic Baeyer-Villiger Oxidation of Cyclohexanone to ε-Caprolactone over Stibium-containing Hydrotalcite" , Catal Lett (2009) 131 :618-623, report the use of stibium (Sb) containing hydrotalcite (typically hydrotalcite has a formula of
Mg2Al2C03(OH)16 · 4 H20) as catalyst in Baeyer-Villiger oxidation of cyclohexanone to ε-caprolactone. The Sb-hydrotalcite catalyst was compared with Fe, Zn, CoFe, Sn, CuFe, TiCu, Cu, Ti and CuFeSb hydrotalcite catalysts. All catalysts except Sb and CuFeSb hydrotalcite gave very low, < 50%, conversion rendering all other tested metal hydrotalcite catalysts as industrially unacceptable and/or inoperable.
Selenium dioxide loaded mordenite (typically mordenite has a formula of Al2Sii0O24 · 7 H20) are in US 4,160,769 disclosed as catalyst in combination with formic acid and selenium dioxide for oxidation of cyclohexanone with hydrogen peroxide yielding a product mixture comprising as low as 58% of ε-caprolactone together with 8.7% of cyclopentanecarboxylic acid.
Furthermore, reaction mechanisms behind enatioselective and asymmetric Baeyer-Villiger oxidations using hydrogen peroxide or 02 as oxidant and organometallic and/or fluorous catalysts are discussed by G-J. ten Brink et al in "The Baeyer-Villiger Reaction: New Development toward Greener Procedures" , Chem. Rev. 2004, 104, 4105-4123.
It has now quite unexpectedly, in view of state of the art, been found that a Baeyer-Villiger oxidation of cyclic ketones, yielding a corresponding lactone in good yield, using hydrogen peroxide as oxidant in presence of at least one catalyst comprising Se, Sn and/or Zn on a carrier material. Sn, Se and/or Zn is/are, in embodiments of the present process, loaded on said carrier material in an amount of, as low as, 0.1-1, such as 0.1-0.7, 0.2-0.5 or 0.3-0.5, mmol/g, calculated as elemental substance on said carrier material. The carrier material is preferably selected from for instance a zeolite, such as a beta zeolite, a ceramic material, such as A1203, or a mesocellular foam. Sn, Se and/or Zn is/are, in embodiments of the present invention, present as a catalytically active organic or inorganic compound and/or as elemental substance and present in said oxidation at a molar ratio Sn, Se and/or Zn, calculated as elemental substance, to reactants, cyclic ketone and hydrogen peroxide, of between 0.001 : 1 and 0.05: 1, such as between 0.003: 1 and 0.3: 1 or between 0.005: 1 and 0.01 : 1. The present process is furthermore optionally performed in presence of at least one azeotropic solvent, such as a non-polar solvent and can be performed as a continuos, a semi-continuos or a batch process.
Said catalyst can be employed as a powder, a spray-powder, a moulding, such as rings, rods, pellets and similar, or any other form known in the art and used in batch mode, semi-continuos mode or continuous mode, such as in a fixed-bed catalyst mode.
Said cyclic ketone is in preferred embodiments of the present invention a saturated lactone, cyclohexanone yielding ε-caprolactone is especially preferred, and said process is preferably performed at a ratio hydrogen peroxide to said cyclic ketone of between 1 : 1 and 1 :3.5.
Said optional azeotropic solvent is, in likewise preferred embodiments, an acetonitrile, a propionitrile, a 1 ,2-dichloroalkane, chloroform, a 1,4-dioxane, a dialkylether, an alkyl acetate and/or an alkyl or dialkyl carbonate. The most preferred solvents include, but is not limited to, 1,4-dioxane and/or methyl tert.butyl ether.
The present process can of course also be performed using a catalyst selected from for instance Mn, Cr, Rh, Ru, Ni, Ca, Na, K, Cu, Ag, Cs, Fe, Ir, Pd, Pt, Al or Ti, as organic or inorganic compound and/or as elemental metal, and/or any combination whereof or wherewith as sole catalyst or as co-catalyst. Said metals or metal compounds, as well as Sn, Se and Zn, can of course also be loaded on any other zeolite, such as a MWW zeolite, any ceramic material, any mesocellular foams or on kiselguhr, carbon, asbestos, chalk or any other carrier known in the art. N-heterocyclic carbenes can, furthermore, be used as co-catalysts.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilise the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following, Examples 1-4 refer to embodiments of the Baeyer-Villiger oxidation according to the present invention and Figure 1 schematically shows a distillation set up as used in said Examples.
Example 1
Hydrogen peroxide (37%) and cyclohexanone (99.9%) were in a ratio 1 :2 fed to a steel tube reactor and reacted in presence of a Zn beta zeolite catalyst, having a Zn content of 0.32 mmol/g, and 1,4-dioxane as azeotropic solvent, yielding ε-caprolactone at a selectivity of 95.2% toward cyclohexanone. Used amount of catalyst was 0.5 mol% calculated as elemental metal and the reaction temperature was 60°C.
Recovery of yielded ε-caprolactone was performed in a destination set up as given in enclosed Figure 1, comprising 4 columns (Figure 1 : 1, 2, 3 and 4), and using a column pressure of 0-1 bar and a column temperature of 5-100°C. The catalyst was filtered off before recovery by distillation. Alternatives to used distillation include for instance so called dividing wall distillation. Unreacted cyclohexanone can of course re-circulated.
Example 2
Example 1 was repeated with the difference that a Sn beta zeolite, having a Sn content of 0.40 mmol/g, was used instead of the Zn catalyst and methyl tert.butyl ether was used as azeotropic solvent instead of 1,4-dioxane. The selectivity toward cyclohexanone was 94.9%. Recovery as in Example 1.
Example 3
Example 1 was repeated with the difference that a Se catalyst, having a Se content of 0.38 mmol/g, on a mesocellular foam was used instead of the Zn catalyst. The selectivity toward cyclohexanone was 94.7%. Recovery as in Example 1.
Example 4
Example 1 was repeated with the difference that a Sn catalyst, having a Sn content of 0.52 mmol/g, on A1203 was used instead of the Zn catalyst. The selectivity toward cyclohexanone was 92.5%. Recovery as in Example 1.
Claims
1. A process for Baeyer-Villiger oxidation of a cyclic ketone yielding a corresponding lactone by oxidation of said cyclic ketone using hydrogen peroxide as oxidant, wherein said oxidation is performed in presence of a catalytically active amount of at least one catalyst comprising Sn, Se and/or Zn loaded in an amount of 0.1-1 mmol/g, calculated as elemental substance, on a carrier material, and optionally in presence of at least one azeotropic solvent.
2. The process according to Claim 1, wherein said amount of Se, Sn and/or Zn, calculated as elemental substance, on said carrier is 0.1-0.7 mmol/g.
3. The process according to Claim 1 or 2, wherein said amount of Se, Sn and/or Zn, calculated as elemental substance, on said carrier is 0.2-0.5 mmol/g.
4. The process according to any of the Claims 1-3, wherein said amount of Se, Sn and/or Zn, calculated as elemental substance, on said carrier is 0.3-0.7 mmol/g.
5. The process according to any of the Claims 1-4, wherein said Sn, Se and/or Zn is present as a catalytically active organic or inorganic compound and/or as elemental substance.
6. The process according to any of the Claims 1-5, wherein said catalyst is present at a molar ratio Sn, Se and/or Zn, calculated as elemental substance, to reactants of between 0.001 : 1 and 0.05: 1.
7. The process according to any of the Claims 1-6, wherein said catalyst is present at a molar ratio Sn, Se and/or Zn, calculated as elemental substance, to reactants of between 0.003:1 and 0.3:1.
8. The process according to any of the Claims 1-7, wherein said catalyst is present at a molar ratio Sn, Se and/or Zn, calculated as elemental substance, to reactants of between 0.005: 1 and 0.01 : 1.
9. The process according to any of the Claims 1-8, wherein said carrier material is a zeolite, a mesocellular foam or a ceramic material.
10. The process according to any of the Claims 1-9, wherein said carrier material is beta zeolite or A1203.
11. The process according to any of the Claims 1-10, wherein said cyclic ketone is cyclohexanone and said lactone is ε-caprolactone.
12. The process according to any of the Claims 1-11 , wherein oxidation is performed at a ratio hydrogen peroxide to cyclic ketone of between 1 : 1 and 1 :3.5.
13. The process according to any of the Claims 1-12, wherein said azeotropic solvent is a non-polar solvent.
14. The process according to any of the Claims 1-13, wherein said optional azeotropic solvent is 1,4-dioxane and/or methyl tert.butyl ether.
15. The process according to any of the Claims 1-14, said process being a continuos, a semi-continuos or a batch process.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818671A (en) * | 2019-11-28 | 2020-02-21 | 浙江大学 | Method for preparing lactone compounds |
| CN112062746A (en) * | 2020-06-11 | 2020-12-11 | 浙江大学 | Method for preparing caprolactone by using in-situ peroxide |
| CN112707883A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of epsilon-caprolactone |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
| CN115385309A (en) * | 2022-09-19 | 2022-11-25 | 西南交通大学 | Preparation method and application of two-dimensional oxygen-doped GaSe nanosheet |
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| CN102452893A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve |
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| CN102452893A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707883A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of epsilon-caprolactone |
| CN112707883B (en) * | 2019-10-25 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of epsilon-caprolactone |
| CN110818671A (en) * | 2019-11-28 | 2020-02-21 | 浙江大学 | Method for preparing lactone compounds |
| CN110818671B (en) * | 2019-11-28 | 2021-04-20 | 浙江大学 | Method for preparing lactone compounds |
| WO2021103798A1 (en) * | 2019-11-28 | 2021-06-03 | 浙江大学 | Method for preparing lactone compound |
| CN112062746A (en) * | 2020-06-11 | 2020-12-11 | 浙江大学 | Method for preparing caprolactone by using in-situ peroxide |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
| CN115385309A (en) * | 2022-09-19 | 2022-11-25 | 西南交通大学 | Preparation method and application of two-dimensional oxygen-doped GaSe nanosheet |
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