CN112774662B - Monoatomic catalyst and preparation method and application thereof - Google Patents
Monoatomic catalyst and preparation method and application thereof Download PDFInfo
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- CN112774662B CN112774662B CN201911065026.3A CN201911065026A CN112774662B CN 112774662 B CN112774662 B CN 112774662B CN 201911065026 A CN201911065026 A CN 201911065026A CN 112774662 B CN112774662 B CN 112774662B
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention particularly relates to a single-atom catalyst and a preparation method and application thereof, wherein the single-atom catalyst is prepared by the following method: (1) preparing MOFs material containing Schiff base functional groups; (2) MOFs material containing Schiff base functional groups and transition metal precursors are combined through coordination bonds and then reduced to prepare the monoatomic catalyst. The prepared catalyst has the characteristics of high selectivity and high activity, and the catalytic activity is basically unchanged after repeated recycling, so that the active metal basically cannot be lost along with the reaction and recycling.
Description
Technical Field
The invention belongs to the technical field of organic catalytic synthesis, and particularly relates to a single-atom catalyst, a preparation method thereof and application thereof in a reaction of directly oxidizing aromatic hydrocarbon and oxygen to generate aromatic ketone.
Background
The reaction for preparing aromatic ketone by side chain methylene oxidation of ethylbenzene and derivatives thereof has wide application prospect and has important significance on the development of petrochemical downstream products, the development of fine chemical engineering and the theoretical research of saturated hydrocarbon bond selective oxidation. Aromatic ketones are raw materials for fine chemicals such as synthetic dyes, perfumes and medicines, and are industrially produced mainly by Friedel-Crafts acylation. However, in Friedel-Crafts reactions, the catalyst AlCl3 generates a large amount of acidic wastewater during hydrolysis, which is harmful to the environment. At present, the industrial preparation of acetophenone by adopting an ethylbenzene air direct oxidation method, namely, the ethylbenzene is catalyzed and oxidized by using a cobalt or manganese-containing mesoporous molecular sieve in an acetic acid medium to obtain the acetophenone yield of 25-30%, but a homogeneous catalytic system can make the catalyst difficult to recover and recycle, a large amount of acidic solvents are easy to corrode, and the conversion rate is low. With the development of catalytic oxidation technology, high conversion rate and high selectivity of oxidation saturated C-H bond are possible. The selective oxidation of aromatic hydrocarbon side chains to prepare aromatic ketones more meets the green chemical requirements and is increasingly attracting attention.
The monoatomic catalyst has high activity and high selectivity, is expected to be used for the selective oxidation of ethylbenzene to produce acetophenone, but has the problem of low dispersity. The metal organic framework material (Metal Organic Frameworks, MOFs) is a porous crystalline material assembled by metal ions and organic ligands, has a very large specific surface area and a highly ordered pore structure, is simple and adjustable in composition and pore size, and is a very potential heterogeneous catalyst carrier. The amino-functionalized MOFs material has the advantages of the MOFs material and an amino functional group, and the introduced amino can be used as an active center of a catalytic reaction, and other active centers required by the catalytic reaction can be introduced by utilizing the post-treatment modification performance of the amino.
The invention utilizes the polycondensation of amino functionalized MOFs material and carbonyl compound to generate organic alkali containing-RC=N-imine group, namely Schiff base, which can form relatively stable coordination metastable state with transition metal ions, and then the catalyst is reduced to obtain the highly dispersed monoatomic catalyst. The method is applied to the reaction of directly oxidizing ethylbenzene to produce acetophenone under the condition of no solvent, and has the characteristics of high activity, high selectivity, high stability and capability of recycling for multiple times.
Disclosure of Invention
The invention aims to provide a single-atom catalyst, which is characterized in that MOFs material containing Schiff base functional groups is prepared, then the MOFs material containing the Schiff base functional groups is coordinated with transition metal precursors, the transition metal precursors are connected to the MOFs material containing the Schiff base functional groups, and then uniform dispersion of transition metals in MOFs structures containing the Schiff base functional groups is realized through reduction. The preparation method is simple and controllable, and can realize the atomic-level dispersion of transition metal on a carrier.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method for preparing a monoatomic catalyst, comprising the following steps:
(1) Adding MOFs material containing amino functional groups into an organic solvent, uniformly mixing, adding an organic ligand, and stirring for reaction, wherein the organic ligand contains carbon groups; washing and drying the reacted product to obtain MOFs material containing Schiff base functional groups;
(2) Adding MOFs material containing Schiff base functional groups into an organic solvent, uniformly mixing, slowly adding a transition metal precursor, and continuously stirring for reaction; washing and drying the reacted product, then pyrolyzing at high temperature, pickling and drying to obtain the single-atom catalyst.
Preferably, the MOFs material containing amino functional groups in the step (1) is any one or more than one of UiO66-NH2, uiO 67-NH2, MIL-125-NH2 and MIL-101-NH 2.
Preferably, the organic ligand in the step (1) is any one or more than one of 2-bipyridyl ketone, pyridine-2-formaldehyde or pyridine-2, 6-dicarboxaldehyde.
Preferably, the organic solvent in the step (1) is any one or more of methanol, ethanol, DMF, toluene, tetrahydrofuran and acetone.
Preferably, the mass ratio of MOFs material containing amino functional groups to organic ligand in step (1) is (10-20): 1.
Preferably, the reaction temperature in the step (1) is 20-30 ℃ and the reaction time is 6-24 h.
Preferably, the washing in step (1) is performed with deionized water for 2 to 3 times.
Preferably, the drying temperature in the step (1) is 50-100 ℃ and the drying time is 12-24 h.
Preferably, the transition metal precursor in the step (2) is acetate of Co, mn.
Preferably, the mass ratio of the transition metal precursor in step (2) to the organic ligand in step (1) is 1: (1-1.25).
Preferably, the organic solvent in the step (2) is any one or any mixture of any several of methanol, ethanol, DMF, toluene, tetrahydrofuran and acetone.
Preferably, the reaction temperature in the step (2) is 20-30 ℃ and the reaction time is 6-24 h.
Preferably, the washing in step (2) is performed with deionized water for 2 to 3 times.
Preferably, the drying temperature in the step (2) is 50-100 ℃ and the drying time is 12-24 h.
Preferably, the high-temperature pyrolysis temperature in the step (2) is 600-800 ℃, the heating rate is 1-10 ℃/min, and the pyrolysis time is 1-3 h.
Preferably, in the step (2), the acid washing matter is any one or more than one of sulfuric acid and hydrofluoric acid, and the concentration is 0.5-5mol/L.
The single-atom catalyst prepared by the method takes MOFs material containing Schiff base functional groups as a carrier and transition metal as an active component, the transition metal is combined with the MOFs material containing the Schiff base functional groups through coordination bonds, and the transition metal is uniformly dispersed on the carrier in an atomic-scale form.
The application of the single-atom catalyst prepared by the method in the reaction of directly oxidizing aromatic hydrocarbon and oxygen to generate aromatic ketone comprises the following steps: aromatic hydrocarbon is used as a raw material, oxygen is used as an oxidant, a single-atom catalyst is used as a heterogeneous catalyst, and the aromatic ketone is generated by stirring reaction under the condition of no solvent.
Preferably, the aromatic hydrocarbon is any one or more of ethylbenzene, 2-methyl ethylbenzene, 2-bromoethylbenzene or 3-bromoethylbenzene.
Preferably, the mass ratio of the aromatic hydrocarbon to the monoatomic catalyst is (20-200): 1.
Preferably, the reaction temperature is 50-150 ℃, the reaction pressure is 0.5-2 MPa, and the reaction time is 1-5 h.
The invention has the beneficial effects that:
1. the preparation method is simple and controllable, and can realize the atomic-level dispersion of the active metal on the carrier.
2. The catalyst of the invention is a heterogeneous catalyst, and the product is easy to separate.
3. The catalyst is applied to the reaction of preparing acetophenone by a method of directly oxidizing ethylbenzene and oxygen, does not need to use a solvent, and is environment-friendly; the method can directly oxidize ethylbenzene to produce acetophenone, has the characteristics of high selectivity and high activity, and the catalytic activity is basically unchanged after repeated recycling, so that active metal is basically not lost along with reaction and recycling.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The preparation method of the monoatomic catalyst comprises the following steps:
(1) Adding MOFs material containing amino functional groups into an organic solvent, uniformly mixing, adding an organic ligand, and stirring for reaction, wherein the organic ligand contains carbon groups; washing and drying the reacted product to obtain MOFs material containing Schiff base functional groups;
(2) Adding MOFs material containing Schiff base functional groups into an organic solvent, uniformly mixing, slowly adding a transition metal precursor, and continuously stirring for reaction; washing and drying the reacted product, then pyrolyzing at high temperature, pickling and drying to obtain the single-atom catalyst.
The MOFs material containing the Schiff base functional group is obtained by forming a mixed solution from the MOFs material containing the amino functional group and the organic ligand containing carbonyl and active nitrogen, and utilizing the reaction of amino in the MOFs material and carbonyl in the organic ligand to connect the organic ligand to the MOFs material; and forming a mixed solution by using the MOFs material containing the Schiff base functional groups and the active metal precursor, coordinating active nitrogen (nitrogen containing lone pair electrons) in the MOFs material containing the Schiff base functional groups with active metal ions in the active metal precursor, connecting the active metal precursor to the MOFs material containing the Schiff base functional groups, and finally realizing uniform dispersion of the active metal components in atomic scale in the MOFs structure through reduction.
Preferably, the MOFs material containing amino functional groups in the step (1) is any one or more than one of UiO66-NH2, uiO 67-NH2, MIL-125-NH2 and MIL-101-NH 2.
Preferably, the organic ligand in the step (1) is any one or more than one of 2-bipyridyl ketone, pyridine-2-formaldehyde or pyridine-2, 6-dicarboxaldehyde.
Preferably, the organic solvent in the step (1) is any one or more of methanol, ethanol, DMF, toluene, tetrahydrofuran and acetone.
Preferably, the mass ratio of the MOFs material containing amino functional groups to the organic ligand in the step (1) is (10-20): 1, for example, can be 10:1, 11: 1. 12:1, 13:1, 14:1, 15: 1. 16:1, 17:1, 18:1, 19:1, 20:1.
preferably, the reaction temperature in step (1) is 20 to 30 ℃, for example, 20 ℃,25 ℃,30 ℃ and the reaction time is 6 to 24 hours, for example, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours, 24 hours.
Preferably, the washing in step (1) is performed with deionized water for 2 to 3 times.
Preferably, the drying temperature in the step (1) is 50 to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, and the drying time is 12 to 24 hours, for example, 12 hours, 15 hours, 18 hours, 21 hours, 24 hours.
Preferably, the transition metal precursor in the step (2) is acetate of Co, mn.
Preferably, the mass ratio of the transition metal precursor in step (2) to the organic ligand in step (1) is 1: (1-1.25).
Preferably, the organic solvent in the step (2) is any one or any mixture of any several of methanol, ethanol, DMF, toluene, tetrahydrofuran and acetone.
Preferably, the reaction temperature in the step (2) is 20 to 30 ℃, for example, 20 ℃,25 ℃,30 ℃ and the reaction time is 6 to 24 hours, for example, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours and 24 hours.
Preferably, the washing in step (2) is performed with deionized water for 2 to 3 times.
Preferably, the drying temperature in the step (2) is 50 to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, and the drying time is 12 to 24 hours, for example, 12 hours, 15 hours, 18 hours, 21 hours, 24 hours.
Preferably, the high temperature pyrolysis temperature in the step (2) is 600-800 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, and the temperature rising rate is 1-10 ℃/min, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, and 100 ℃/min, and the pyrolysis time is 1-3 hours, for example, 1 hour, 2 hours, and 3 hours.
Preferably, in the step (2), the acid-washing substance is one or a mixture of more than one of sulfuric acid and hydrofluoric acid, and the concentration is 0.5-5mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min and 5 ℃/min.
The single-atom catalyst prepared by the method takes MOFs material containing Schiff base functional groups as a carrier and transition metal as an active component, the transition metal is combined with the MOFs material containing the Schiff base functional groups through coordination bonds, and the transition metal is uniformly dispersed on the carrier in an atomic-scale form.
The application of the single-atom catalyst prepared by the method in the reaction of directly oxidizing aromatic hydrocarbon and oxygen to generate aromatic ketone comprises the following steps: aromatic hydrocarbon is used as a raw material, oxygen is used as an oxidant, a single-atom catalyst is used as a heterogeneous catalyst, and the aromatic ketone is generated by stirring reaction under the condition of no solvent.
Preferably, the aromatic hydrocarbon is any one or more of ethylbenzene, 2-methyl ethylbenzene, 2-bromoethylbenzene or 3-bromoethylbenzene.
Preferably, the mass ratio of the aromatic hydrocarbon to the monoatomic catalyst is (20-200): 1.
Preferably, the reaction temperature is 50-150 ℃, the reaction pressure is 0.5-2 MPa, and the reaction time is 1-5 h.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto. The experimental methods in the examples are all conventional methods unless otherwise specified; the materials used, unless otherwise specified, are all commercially available from conventional biochemical reagent manufacturers.
Example 1
1g of UiO66-NH2 is taken and added into 50mL of methanol, after being uniformly mixed, 0.05g of pyridine-2-formaldehyde is added, and stirring reaction is carried out for 6 hours at 20 ℃; washing the reacted product with deionized water, and drying at 50 ℃ for 24 hours to obtain MOFs material containing Schiff base functional groups; adding MOFs material containing Schiff base functional groups into 50mL of methanol, uniformly mixing, slowly adding 10mL of 4g/L methanol solution of manganese acetate, and stirring at 20 ℃ for reaction for 6h; washing the reacted product with deionized water, drying at 50 ℃ for 24 hours, pyrolyzing at 600 ℃ for 1 hour, washing with 0.5mol/L sulfuric acid, and finally drying at 50 ℃ for 24 hours to obtain the monoatomic catalyst.
Example 2
1g of UiO66-NH2 is taken and added into 50mL of ethanol, after being uniformly mixed, 0.1g of 2-bipyridyl ketone is added, and the mixture is stirred at 30 ℃ for reaction for 24 hours; washing the reacted product with deionized water, and drying at 100 ℃ for 12 hours to obtain MOFs material containing Schiff base functional groups; adding MOFs material containing Schiff base functional groups into 50mL of ethanol, uniformly mixing, slowly adding 10mL of 100g/L ethanol solution of cobalt acetate, and stirring at 30 ℃ for reaction for 24 hours; washing the reacted product with deionized water, drying at 100 ℃ for 12 hours, then carrying out high-temperature pyrolysis at 800 ℃ for 5 hours, washing with 5mol/L sulfuric acid, and finally drying at 100 ℃ for 12 hours to obtain the monoatomic catalyst.
Example 3
1g of UiO66-NH2 is taken and added into 50mL of methanol, after being uniformly mixed, 0.1g of pyridine-2, 6-dicarboxaldehyde is added, and stirring reaction is carried out for 12h at 25 ℃; washing the reacted product with deionized water, and drying at 100 ℃ for 12 hours to obtain MOFs material containing Schiff base functional groups; adding MOFs material containing Schiff base functional groups into 50mL of ethanol, uniformly mixing, slowly adding 10mL of 30g/L ethanol solution of cobalt acetate, and stirring at 25 ℃ for reaction for 12h; washing the reacted product with deionized water, drying at 100 ℃ for 12 hours, then carrying out high-temperature pyrolysis at 800 ℃ for 2 hours, washing with 1mol/L sulfuric acid, and finally drying at 100 ℃ for 12 hours to obtain the monoatomic catalyst.
Example 4
1g of UiO66-NH2 is taken and added into 50mL of methanol, after being uniformly mixed, 0.1g of pyridine-2, 6-dicarboxaldehyde is added, and stirring reaction is carried out for 12h at 25 ℃; washing the reacted product with deionized water, and drying at 100 ℃ for 12 hours to obtain MOFs material containing Schiff base functional groups; adding MOFs material containing Schiff base functional groups into 50mL of ethanol, uniformly mixing, slowly adding 10mL of 30g/L ethanol solution of manganese acetate, and stirring at 25 ℃ for reaction for 12h; washing the reacted product with deionized water, drying at 100 ℃ for 12 hours, then carrying out high-temperature pyrolysis at 800 ℃ for 2 hours, washing with 1mol/L sulfuric acid, and finally drying at 100 ℃ for 12 hours to obtain the monoatomic catalyst.
The single-atom catalysts of examples 1-4 were used in the direct oxidation of styrene with oxygen to acetophenone, which was carried out in a 50mL flask under the following conditions: 4g of ethylbenzene, 0.04g of catalyst, oxygen (5 mL/min) as reaction gas, 130 ℃ as reaction temperature and 4h as reaction time. After the reaction was completed, the reaction mixture was cooled to room temperature, and the centrifugally separated filtrate was quantitatively detected by using gas chromatography of Shimadzu GC-2014C.
The results are shown in Table 1.
Table 1: catalyst Performance test data
As can be seen from Table 1, the monoatomic catalyst of the invention is used in the reaction for preparing acetophenone by ethylbenzene oxidation, has the characteristics of high activity and high selectivity, is repeatedly used for a plurality of times, does not generate sintering agglomeration phenomenon, does not obviously reduce activity and selectivity, and has the characteristics of high stability.
The above embodiments are described in detail with respect to the technical solution of the present invention. It is obvious that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes thereto, but any changes equivalent or similar to the present invention are within the scope of the present invention.
Claims (2)
1. A method for preparing a monoatomic catalyst, comprising the following steps:
(1) Adding MOFs material containing amino functional groups into an organic solvent, uniformly mixing, adding an organic ligand, and stirring for reaction, wherein the organic ligand contains carbonyl; washing and drying the reacted product to obtain MOFs material containing Schiff base functional groups; the MOFs material containing the amino functional group is any one or more than one of UiO-67-NH2 and MIL-125-NH 2; the organic ligand is any one or more than one of 2-bipyridyl ketone, pyridine-2-formaldehyde or pyridine-2, 6-dicarboxaldehyde; the mass ratio of the MOFs material containing the amino functional group to the organic ligand is (10-20): 1;
(2) Adding MOFs material containing Schiff base functional groups into an organic solvent, uniformly mixing, slowly adding a transition metal precursor, and continuously stirring for reaction; the transition metal precursor is acetate of Co and Mn, and the mass ratio of the transition metal precursor to the organic ligand in the step (1) is 1: (1-1.25); washing and drying the reacted product, then carrying out high-temperature pyrolysis, acid washing and drying to obtain a single-atom catalyst; the high-temperature pyrolysis temperature is 600-800 ℃, the heating rate is 1-10 ℃/min, and the high-temperature pyrolysis time is 1-3 h; the acid washing matter is one or more than one of sulfuric acid and hydrofluoric acid, and the concentration is 0.5-5 mol/L;
the single-atom catalyst takes MOFs material containing Schiff base functional groups as a carrier and transition metal as an active component, the transition metal and the MOFs material containing the Schiff base functional groups are combined through coordination bonds, and the transition metal is uniformly dispersed on the carrier in an atomic-scale form;
the application of the single-atom catalyst in the reaction of directly oxidizing aromatic hydrocarbon and oxygen to generate aromatic ketone comprises the following steps: aromatic hydrocarbon is used as a raw material, oxygen is used as an oxidant, a single-atom catalyst is used as a heterogeneous catalyst, and the aromatic ketone is generated by stirring reaction under the condition of no solvent.
2. The preparation method according to claim 1, wherein the organic solvent in the steps (1) and (2) is any one or any mixture of any several of methanol, ethanol, DMF, toluene, tetrahydrofuran and acetone.
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