CN112354551B - Monoatomic metal photocatalyst, preparation method thereof and application thereof in carbon-oxygen cross-coupling reaction - Google Patents

Monoatomic metal photocatalyst, preparation method thereof and application thereof in carbon-oxygen cross-coupling reaction Download PDF

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CN112354551B
CN112354551B CN202011270835.0A CN202011270835A CN112354551B CN 112354551 B CN112354551 B CN 112354551B CN 202011270835 A CN202011270835 A CN 202011270835A CN 112354551 B CN112354551 B CN 112354551B
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alcohol
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CN112354551A (en
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赵进才
刘天骄
宋文静
赵鑫
孟涤
籍宏伟
马万红
陈春城
车延科
盛桦
章宇超
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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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the field of photocatalysis/metal catalysis organic synthesis, and provides a carbon-based single-atom metal catalytic material, a preparation method and application thereof. The catalyst comprises a graphite type carbon nitride substrate, a metal center and a sheet form with uniformly distributed metal atoms, wherein the metal is anchored on the surface of the substrate in the form of ions. The catalyst developed by the invention has the advantages of low reaction temperature, high conversion rate, wide applicable substrate range, less side reaction and the like, and particularly has obvious advantages compared with the existing catalyst in the aspects of conversion number, metal utilization efficiency, preparation cost and recycling.

Description

Monoatomic metal photocatalyst, preparation method thereof and application thereof in carbon-oxygen cross-coupling reaction
Technical Field
The invention relates to the field of photo/metal catalytic synthesis, in particular to the research and development of a monatomic metal photocatalyst for synthesizing ether/phenol by cross carbon-oxygen coupling.
Background
The cross coupling reaction of carbon, oxygen, carbon and nitrogen is an important reaction for preparing medicines and fine chemical products. The traditional catalyst mainly comprises a metal palladium complex, and the ligand structure is complex; in addition, strong organic bases such as potassium tert-butoxide and the like are required or the reaction is completed by raising the temperature. An important breakthrough in the catalytic system for the heterocoupling reaction in recent years is the realization of the coupling reaction driven by light by combining photocatalysis and metal catalysis. The photocatalyst can be selected from molecular dye or semiconductor material, the first transition metal complex is used for replacing noble metal palladium, the ligand structure is relatively simple, and strong base assistance is not needed. The core reaction step is that photoinduced electron or energy transfer triggers the change of metal valence state, thereby giving the coupling product through oxidative addition-reduction elimination. The electron or energy transfer efficiency in the initiation step is limited, the speed of the light-driven coupling reaction needs to be further improved, and in addition, higher metal complex dosage is usually required in the reaction, so that the problems of metal deposition inactivation, poor cyclic utilization rate and the like exist.
Disclosure of Invention
The invention provides a monoatomic metal photocatalytic material, which is in a lamellar form with uniformly distributed metal atoms; the metal is ionically supported on the substrate surface and the metal loading may be 0.04 to 0.36 wt%, for example 0.1 to 0.2 wt%, illustratively 0.11 wt%.
According to an embodiment of the present invention, the method for preparing the monatomic metallic photocatalytic material includes the steps of:
step (1): heating and calcining the small-molecule precursor by a program to obtain a graphite type carbon nitride substrate;
step (2): and (2) dispersing the substrate in the step (1) in a polar organic solution of metal salt, and reacting to obtain the monatomic metal photocatalytic material.
According to an embodiment of the present invention, the small molecule precursor in step (1) may be at least one selected from urea, cyanamide, dicyandiamide, melamine;
according to an embodiment of the invention, in step (1), the calcination is preferably carried out in a muffle furnace; the calcination time may be 1-5h, e.g. 2h, and the temperature rise rate is 1-5 deg.C/min, e.g. 2 deg.C/min.
According to an embodiment of the present invention, step (1) further comprises the steps of washing and drying the substrate after the calcination; the cleaning step is that ethanol and water are used for cleaning for a plurality of times in sequence; the drying time may be 2-24h, for example 12 h.
According to an embodiment of the present invention, in the step (2), the metal salt may be a nickel salt, such as nickel chloride, nickel nitrate, nickel sulfate, tetrasodium salt of nitinol tetrasulfonic acid, or respective hydrates thereof;
according to an embodiment of the present invention, in the step (2), the polar organic solvent may be selected from at least one of dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, or dimethylsulfoxide;
according to an embodiment of the present invention, in the step (2), the mass ratio of the metal salt to the substrate may be (1-60):500, for example (20-60): 500.
According to an embodiment of the invention, in step (2), the concentration of the metal salt in the polar organic solvent may be from 0.02 to 5mmol/L, for example from 0.05 to 2mmol/L, exemplarily 1 mmol/L;
according to an embodiment of the invention, in step (2), the concentration of the substrate in the polar organic solvent is 1-5g/L, such as 2 g/L.
According to an embodiment of the invention, in step (2), the reaction time may be 1 to 12h, for example 6 h;
according to an embodiment of the present invention, the step (2), after the reaction, further comprises washing with a reaction solvent at least twice; after washing, drying is carried out for 2 to 24 hours, for example 12 hours.
The invention also provides application of the monatomic metal photocatalytic material as a photocatalyst.
The invention also provides a photocatalyst which comprises the monatomic metal photocatalytic material.
The invention also provides a catalyst composition comprising the photocatalyst and an ancillary ligand.
According to an embodiment of the present invention, the ancillary ligand may be an azaaryl compound, for example, at least one selected from the group consisting of pyridine, imidazole, aminoimidazole, bipyridine, pyrrole, pyrazole, and pyrimidine;
the invention also provides application of the photocatalyst and/or the catalyst composition in carbon-oxygen cross-coupling reaction, such as application in catalyzing reaction of halogenated hydrocarbon and alcohol to prepare ether or phenol.
According to an embodiment of the present invention, the halogenated hydrocarbon may be a halogenated aromatic compound, such as p-bromoacetophenone, p-bromotrifluorotoluene, p-bromobenzonitrile, p-bromobenzaldehyde, ethyl p-bromobenzoate, m-bromoacetophenone, 4-methylbenzophenone, 5-bromo-2-cyanopyridine or bromobenzene;
according to an embodiment of the invention, the alcohol may be a primary or secondary alcohol, such as methanol, ethanol, trifluoroethanol, benzyl alcohol, isopropanol.
According to an embodiment of the present invention, the catalytic halogenated hydrocarbon and alcohol ether or phenol production reaction comprises the following steps:
adding a photocatalyst, an auxiliary ligand, a halogenated aromatic compound, organic base, alcohol or water and an organic solvent into a photoreactor, irradiating by more than 400nm, and purifying after reaction to obtain a product.
According to an embodiment of the present invention, the photoreactor is preferably a light-transmitting reactor, such as a Pyrex glass reactor; further preferably, the photocatalytic reactor is sealed to remove oxygen.
According to an embodiment of the present invention, the concentration of the photocatalyst in the reaction system is 0.5 to 10g/L, preferably 2 g/L;
according to an embodiment of the present invention, the concentration of the ancillary ligand in the reaction system is 0.0003 to 0.02mol/L, preferably 0.004 mol/L;
according to an embodiment of the present invention, the concentration of the halogenated aromatic compound in the reaction system is 0.002 to 0.06mol/L, preferably 0.02 mol/L;
according to an embodiment of the invention, the molar ratio of the halogenated aromatic compound to the alcohol is from 1:20 to 100, such as from 1:40 to 80, exemplary from 1: 60;
according to embodiments of the present invention, the molar ratio of the halogenated aromatic compound to the organic base may be from 1:0.5 to 5, such as from 1:1 to 3, illustratively 1: 1.8;
according to an embodiment of the present invention, the organic solvent may be selected from at least one of dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, or dimethylsulfoxide;
according to embodiments of the invention, the reaction temperature may be 10-40 ℃, e.g. 25 ℃; the irradiation time may be 6h or more, examples 6h, 8h, 12 h; preferably, the irradiation is carried out under stirring.
Advantageous effects
The invention designs a single atom metal photocatalysis material and a catalyst composition prepared from the same by utilizing coordination of a carbon nitride-rich coordination nitrogen site and a metal, wherein a substrate and the metal are connected through a chemical bond in the catalyst, so that the electron transfer and the catalyst activation between the substrate and the metal are promoted; and further combining with a small molecule auxiliary ligand to construct an active metal center for carbon-oxygen cross coupling of a halogenated aromatic compound driven by visible light and alcohol/water to obtain ether or phenol and a recovered photocatalyst. The coupling of electron-deficient halogenated aromatic compound and alcohol/water is realized under mild conditions with high conversion number, the metal consumption is reduced on the premise of ensuring high selectivity of coupling products, the atomic efficiency is improved, the deposition inactivation is avoided, and the recycling of the catalyst is realized.
Drawings
Fig. 1 is a Ni element distribution of the catalyst prepared in example 1.
FIG. 2 is X-ray photoelectron spectroscopy (XPS) spectra of N1s (left) and Ni 2p (right) of the catalyst prepared in example 1.
FIG. 3 shows the catalyst prepared in example 1 and C3N4The emission spectrum of (2).
FIG. 4 is the gas spectrum of the product of the coupling reaction of p-bromoacetophenone and methanol in example 2.
FIG. 5 is a nuclear magnetic diagram of the product of the methanol coupling reaction of p-bromoacetophenone in example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
10g of urea was heated to 500 ℃ at a heating rate of 2 ℃/min and kept at 500 ℃ in air for 2 hours. The yellow solid product obtained was triturated and washed with water and ethanol. The sample was dried under vacuum for 12h to give C3N4. By mixing 1mmol/L of nickel chloride hexahydrate and C3N4(2g/L) was dispersed in a suspension of 50mL DMAc, and reacted for 6 hours. It was then centrifuged and the solid product washed twice and then dried in vacuo for 12 h. To obtain C3N4Carrying mononuclear nickel.
Example 2
Mixing 10mg of C3N4Ni, 0.02mmol of auxiliary ligand imidazole, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol are added into (DMAc), and the total volume of the reaction solution is 5 mL. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The photoreaction was performed under irradiation of a xenon lamp equipped with a 400nm stop filter. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8h of irradiation, the product p-methoxyacetophenone was obtained in 97% yield.
Comparative example 1
Mixing 10mg of C3N4Ni with 0.02mmol of the ancillary ligand imidazole, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol were added to 5mL of DMAc. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8 hours of reaction without light, no reactant conversion and no p-methoxyacetophenone are generated.
Comparative example 2
Mixing 10mg of C3N4Ni, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol were added to (DMAc) and the total volume of the reaction solution was 5 mL. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The photoreaction was performed under irradiation of a xenon lamp equipped with a 400nm stop filter. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8h of irradiation, the product p-methoxyacetophenone was obtained in 6% yield.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. The use of a catalyst composition for catalysing the reaction of a halogenated hydrocarbon and an alcohol to produce an ether or a phenol;
the catalyst composition comprises a monatomic metal photocatalytic material and ancillary ligands;
the monatomic metal photocatalytic material is in a lamellar form with uniformly distributed metal atoms; the metal is loaded on the surface of the substrate in the form of ions, and the metal loading is 0.04-0.36 wt%;
the auxiliary ligand is selected from at least one of pyridine, imidazole, aminoimidazole, bipyridine, pyrrole, pyrazole and pyrimidine;
the halogenated hydrocarbon is selected from bromoacetophenone, bromotrifluorotoluene, bromobenzonitrile, bromobenzaldehyde, ethyl bromobenzoate, bromoacetophenone, 4-methylbenzophenone, 5-bromo-2-cyanopyridine or bromobenzene;
the alcohol is selected from methanol, ethanol, trifluoroethanol, benzyl alcohol and isopropanol;
the preparation method of the monatomic metal photocatalytic material comprises the following steps:
step (1): heating and calcining the small-molecule precursor by a program to obtain a graphite type carbon nitride substrate;
step (2): dispersing the substrate in the step (1) in a polar organic solution of metal salt, and reacting to obtain the monatomic metal photocatalytic material;
the micromolecular precursor in the step (1) is selected from at least one of urea, cyanamide, dicyandiamide and melamine;
in the step (2), the metal salt is selected from nickel chloride, nickel nitrate, nickel sulfate, nickel phthalocyanine tetrasulfonic acid tetrasodium salt or respective hydrates thereof;
in the step (2), the polar organic solvent used in the polar organic solution is at least one selected from dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, and dimethylsulfoxide.
2. Use according to claim 1, characterized in that in step (1), the calcination is carried out in a muffle furnace; the calcination time is 1-5h, and the heating rate is 1-5 ℃/min;
in the step (1), after the calcination, the method further comprises the steps of cleaning and drying the substrate; the cleaning step is that ethanol and water are used for cleaning for a plurality of times in sequence; the drying time is 2-24 h.
3. The use according to claim 1 or 2, wherein in step (2), the mass ratio of the metal salt to the substrate is (1-60): 500;
in the step (2), the concentration of the metal salt in the polar organic solvent is 0.02-5 mmol/L;
in the step (2), the concentration of the substrate in the polar organic solvent is 1-5 g/L;
in the step (2), the reaction time is 1-12 h;
in the step (2), after the reaction, washing at least twice by using a reaction solvent; and (4) cleaning and drying for 2-24 h.
4. The use according to claim 1 or 2, wherein in step (2), the mass ratio of the metal salt to the substrate is (20-60): 500;
in the step (2), the concentration of the metal salt in the polar organic solvent is 0.05-2 mmol/L.
5. Use according to claim 1 or 2, characterized in that said catalytic reaction of halogenated hydrocarbons with alcohols to produce ethers or phenols comprises the following steps:
adding a photocatalyst, an auxiliary ligand, halogenated hydrocarbon, organic base, alcohol and an organic solvent into a photoreactor, irradiating by using light with the wavelength of more than 400nm, and purifying after reaction to obtain a product;
the concentration of the photocatalyst in the reaction system is 0.5-10 g/L;
the concentration of the auxiliary ligand in the reaction system is 0.0003-0.02 mol/L;
the concentration of the halogenated hydrocarbon in the reaction system is 0.002-0.06 mol/L;
the molar ratio of the halogenated hydrocarbon to the alcohol is 1: 20-100;
the molar ratio of the halogenated hydrocarbon to the organic base is 1: 0.5-5.
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CN115090327B (en) * 2022-06-10 2023-06-16 中国科学院化学研究所 Covalent organic framework photocatalytic material with controllable coordination site number and loaded with metal monoatoms, and preparation method and application thereof

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