Method for preparing phenol or ether compound through photocatalysis

Abstract

The invention provides a method for preparing phenol or ether compounds through photocatalysis, which comprises the following steps: in the presence of a carbon nitride material subjected to surface hydroxylation treatment and a compound containing a nickel element, effectively activating water or alcohol through photocatalysis under the condition of not adding an organic amine sacrificial agent, and realizing a cross-coupling reaction of aryl halide and water or alcohol. According to the catalytic method, visible light can be utilized for reaction under mild conditions, and the performance of converting aryl halide into phenol or ether can be remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of photocatalysis, and in particular to a method for preparing phenol or ether compounds by photocatalysis. Background Art

[0002] Phenolic compounds are a class of organic intermediates with a wide range of uses, and they have important applications in drug preparation and fine chemical synthesis. Similarly, ether compounds, which are widely present in nature and synthetic compounds, have important applications in medicine, chemistry, manufacturing and industry. The oxidation method of isopropylbenzene or the hydrolysis method of halogenated benzene commonly used in the industry to prepare phenolic compounds have problems such as complex process, high energy consumption, high cost and environmental unfriendliness. The Ullmann and Williamson synthesis methods commonly used to synthesize ether compounds also often require harsh conditions such as high temperature and strong alkali. Therefore, achieving a more efficient, simple and environmentally friendly synthesis of phenolic / ether compounds is an inevitable requirement for green organic process production.

[0003] The metal / light dual catalytic system developed in recent years can realize green cross-coupling reactions in a mild system. In the photocatalytic cross-coupling reaction, aromatic halogenated compounds are common reaction building block molecules, dye molecules or semiconductor materials with light absorption properties are classic photocatalysts, and cheap first transition metals are common metal reaction centers. Among them, photoactive metal organic framework materials (MOFs), metal oxides, carbon nitrides and covalent organic frameworks (COFs) loaded with metals such as iron, cobalt, nickel, and copper are widely used in photocatalytic cross-coupling reactions due to their advantages such as reusability. Carbon nitride (CN) is an organic semiconductor material that is simple to prepare, low in cost, has good photostability and has visible light response. At the same time, it is rich in nitrogen coordination sites and is easy to modify metals through coordination. These advantages give it broad application prospects. However, common carbon nitride materials have the disadvantages of easy recombination of photogenerated carriers, low visible light utilization efficiency, and limited reaction sites. They often need to be modified, and the treatment of carbon nitride to improve its activity is cumbersome and not reproducible enough. Therefore, a simple and reliable synthesis method is needed to modify carbon nitride. The photocatalytic research system reported so far for the conversion of halogenated aromatics to phenols / ethers still requires the addition of physiologically toxic organic amines as sacrificial agents, which deviates from the goal of green synthesis. Summary of the invention

[0004] The present invention develops a photocatalytic material with low cost, high atomic utilization rate and simple synthesis, which uses water / alcohol as a sacrificial agent and a reaction raw material to effectively convert halogenated aromatic hydrocarbons into phenolic / etheric compounds in a simple and mild system. Specifically, the present invention provides a catalyst composition (including a carbon nitride material with a surface hydroxylation treatment and a compound containing a nickel element), in the presence of which, water or alcohol can be effectively photocatalytically activated without adding an organic amine sacrificial agent, to achieve a cross-coupling reaction of halogenated aromatic hydrocarbons with water or alcohol. The catalytic method can react using visible light under mild conditions and can significantly improve the performance of converting halogenated aromatic hydrocarbons into phenols or ethers.

[0005] The invention provides a catalyst composition, which comprises: a hydroxylated carbon nitride material and a compound containing nickel element.

[0006] According to an embodiment of the present invention, the catalyst composition is used for photocatalytic reaction of halogenated aromatic hydrocarbons with water to generate phenolic compounds or for photocatalytic reaction of halogenated aromatic hydrocarbons with alcohol substances to generate aromatic ether compounds.

[0007] According to an embodiment of the present invention, the reaction of generating a phenolic compound or the reaction of generating an aromatic ether compound is performed in the presence of a base.

[0008] According to an embodiment of the present invention, the base is an inorganic base or an organic base, preferably an inorganic base.

[0009] According to an embodiment of the present invention, the halogenated aromatic hydrocarbon is an iodinated aromatic hydrocarbon, a brominated aromatic hydrocarbon or a chlorinated aromatic hydrocarbon.

[0010] According to an embodiment of the present invention, the aromatic hydrocarbon is selected from C 6-20 Aromatic hydrocarbons or 5-20 membered heteroaromatic hydrocarbons.

[0011] According to an embodiment of the present invention, the C 6-20 The aromatic hydrocarbon or 5-20 membered heteroaromatic hydrocarbon may be optionally substituted by one, two or more groups Rs which are inert to the photocatalytic reaction, wherein Rs is selected from the following groups: CN, CHO, C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC 1-12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl; said C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20The aryl or 5-20 membered heteroaryl group is further optionally substituted by one, two or more groups Ra which are inert to the photocatalytic reaction, wherein Ra is selected from the following groups: CN, CHO, C 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, -COC 1-12 Alkyl or -COOC 1-12 alkyl.

[0012] For example, Rs is CN, CHO, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, -COC 1-6 Alkyl, -COOC 1-6 Alkyl, C 3-12 Cycloalkyl, 3-12 membered heterocyclic group, C 6-14 Aryl or 5-14 membered heteroaryl, such as CN, CHO, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, -COCH3, -COOCH3.

[0013] According to an embodiment of the present invention, the number of iodine, bromine or chlorine halide ions in the iodinated aromatic hydrocarbon, the brominated aromatic hydrocarbon or the chlorinated aromatic hydrocarbon is 1 or more, for example, 1, 2, 3, 4, 5 or 6.

[0014] For example, the halogenated aromatic hydrocarbon is at least one of iodobenzene, bromobenzene, chlorobenzene, p-iodoacetophenone, p-bromoacetophenone, p-chloroacetophenone, p-iodobenzonitrile, p-bromobenzonitrile, p-chlorobenzonitrile, p-iodobenzotrifluoride, p-bromobenzotrifluoride, p-iodobenzaldehyde, p-bromobenzaldehyde, p-chlorobenzaldehyde, methyl p-bromobenzoate, and m-bromoacetophenone.

[0015] According to an embodiment of the present invention, the halogenated aromatic hydrocarbon and the alcohol substance undergo an effective carbon-oxygen cross-coupling reaction to generate aromatic ether compounds, and the alcohol substance is a monohydric alcohol with a carbon number less than 10, such as at least one of methanol, ethanol, propanol, n-butanol, etc.

[0016] According to an embodiment of the present invention, the nickel-containing compound can be added to the photocatalytic reaction system separately from the hydroxylated carbon nitride material, or the nickel-containing compound can be loaded onto the hydroxylated carbon nitride material and then added to the system as a nickel-loaded hydroxylated carbon nitride material for photocatalytic reaction.

[0017] According to an embodiment of the present invention, the hydroxylated carbon nitride is a nano-organic semiconductor material.

[0018] According to an embodiment of the present invention, the hydroxylated carbon nitride material is represented by CN-OH, which can be prepared by a method comprising the following preparation steps:

[0019] Step (1): selecting a small molecule precursor rich in carbon and nitrogen, subjecting the precursor to self-assembly treatment or no treatment, and then subjecting the precursor to high-temperature calcination and thermal polymerization to obtain ordinary carbon nitride;

[0020] Step (2): subjecting the ordinary carbon nitride obtained in step (1) to hydrothermal treatment.

[0021] Preferably, the carbon-nitrogen rich small molecule precursor in step (1) can be selected from one, two or more of thiourea, cyanamide, dicyandiamide, melamine, urea and cyanuric acid, preferably urea alone.

[0022] Preferably, the calcination temperature is 500-600°C, preferably 550°C.

[0023] Preferably, the calcination time is 1 to 12 hours, such as 2 to 6 hours, preferably 4 hours.

[0024] Preferably, the heating rate of the calcination is 1-10°C / min, preferably 5°C / min.

[0025] Furthermore, after the calcination is completed, the calcined product is ground.

[0026] Preferably, in step (2), ordinary carbon nitride is taken and added to an aqueous solution with a pH of 1 to 13 (adjusted by HCl and NaOH) and stirred, and the pH of the aqueous solution is preferably 7.

[0027] Preferably, the mass ratio of the carbon nitride to the aqueous solution is 1:(100-500), preferably 1:100.

[0028] Preferably, the hydrothermal treatment in step (2) is carried out in a reactor. Specifically, the temperature of the hydrothermal reaction is 120-200°C, preferably 160°C; the time of the hydrothermal reaction is 4-20 hours, preferably 10 hours.

[0029] In some embodiments of the present invention, after the hydrothermal treatment, a process of solid-liquid separation, washing and drying to obtain the product is also included.

[0030] According to an embodiment of the present invention, the solid-liquid separation can be obtained by freeze-drying after centrifugation for a small amount of material; and can be obtained by drying in a drying oven after filtration for a large amount of preparation.

[0031] According to an embodiment of the present invention, the cleaning needs to be performed using an organic solvent and water, preferably ethanol and water, and the cleaning is performed at least three times respectively.

[0032] According to an embodiment of the present invention, the cleaning is followed by drying in a vacuum oven for 1 to 48 hours.

[0033] According to an embodiment of the present invention, the nickel-loaded hydroxylated carbon nitride material is represented by Ni / CN-OH, which can be prepared by a method comprising the following synthesis steps:

[0034] Step (1a): Grind the above hydroxylated carbon nitride material (expressed as CN-OH) to obtain a powdered solid, disperse it in a solvent and perform ultrasonic dispersion to obtain a carbon nitride nanosheet suspension; then add a nickel-containing compound, optionally with or without an organic amine, and stir to obtain a mixed solution;

[0035] Step (2a): placing the mixed solution obtained in step (1a) into a microwave reactor for reaction to obtain a nickel-loaded hydroxylated carbon nitride-based material.

[0036] According to an embodiment of the present invention, the compound containing nickel element can be selected from one, two or more of nickel sulfate, nickel bromide, nickel acetate, nickel nitrate, nickel chloride, nickel acetylacetonate, nickel perchlorate and hydrates thereof (such as nickel nitrate hexahydrate, nickel acetylacetonate dihydrate, nickel chloride hexahydrate, etc.), preferably nickel chloride hexahydrate.

[0037] According to an embodiment of the present invention, the mass ratio of the compound containing nickel element to CN—OH is 1:(10-2000), preferably 1:(20-500), and exemplarily 5:100.

[0038] According to an embodiment of the present invention, the organic amine can be selected from at least one of triethanolamine, diisopropanolamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane and N,N-diisopropylethylamine. The organic amine can promote the deposition of the nickel-containing compound on the carbon nitride support, and its presence is conducive to the slow dissolution of the nickel-containing compound and the effective coordination with the nitrogen site on the surface of the carbon nitride to generate active sites; the organic amine may also not be added to the aqueous solution.

[0039] According to an embodiment of the present invention, the molar ratio of the compound containing nickel element to the organic amine is (1:10-300), for example (1:10-50), and exemplarily 1:22.

[0040] According to an embodiment of the present invention, the solvent in step (1a) can be water or an organic solvent, preferably methanol, ethanol, acetonitrile, exemplified by acetonitrile.

[0041] According to an embodiment of the present invention, the stirring time is 0.5-4 hours, so that the nickel-containing compound and the hydroxylated carbon nitride material suspension are mixed evenly.

[0042] According to an embodiment of the present invention, the microwave heating temperature is 40-90° C., and the microwave time is 1-8 h.

[0043] According to an embodiment of the present invention, after the reaction in the microwave reactor is completed, the step of performing solid-liquid separation on the reaction system is further included, for example, centrifugation or filtration.

[0044] The present invention also provides the use of the catalyst composition for photocatalytic reaction of halogenated aromatic hydrocarbons with water to generate phenolic compounds, or for photocatalytic reaction of halogenated aromatic hydrocarbons with alcohol substances to generate aromatic ether compounds.

[0045] The present invention also provides a method for preparing phenolic compounds or aromatic ether compounds, comprising the following steps: subjecting halogenated aromatic hydrocarbons and water or alcohol substances to a light irradiation reaction in the presence of the above catalyst composition.

[0046] According to an embodiment of the present invention, the method comprises the following steps: subjecting halogenated aromatic hydrocarbons to a light reaction with water in the presence of the above-mentioned catalyst composition to obtain a phenolic compound; or, subjecting halogenated aromatic hydrocarbons to a light reaction with an alcohol substance in the presence of the above-mentioned catalyst composition to a light reaction to obtain an aromatic ether compound.

[0047] According to an embodiment of the present invention, the photoirradiation reaction is carried out under an inert gas atmosphere, for example, in the presence of nitrogen or argon.

[0048] According to an embodiment of the present invention, the molar ratio of the nickel-containing compound to the substrate halogenated aromatic hydrocarbon is 1:(5-1000), such as 1:(10-100), exemplarily 1:5, 1:10, 1:50, 1:250, 1:500, preferably 1:50.

[0049] According to an embodiment of the present invention, the photo-irradiation reaction is carried out in the presence of a base, such as an inorganic base or an organic base, preferably in the presence of an inorganic base.

[0050] According to an embodiment of the present invention, the molar ratio of the base to the halogenated aromatic hydrocarbon is (1-50):1, for example (1-30):1, such as 2:1.

[0051] According to an embodiment of the present invention, the reaction of halogenated aromatics with water to produce phenols by carbon-oxygen cross-coupling specifically includes: under the condition that a compound containing a nickel element and a hydroxylated carbon nitride material are added separately or directly added to a hydroxylated carbon nitride-based material Ni / CN-OH loaded with nickel, the halogenated aromatics and water react to prepare a phenolic compound.

[0052] According to an embodiment of the present invention, the halogenated aromatic hydrocarbon and water or an alcohol substance undergo a carbon-oxygen cross-coupling reaction, which specifically comprises the following steps:

[0053] The photocatalyst hydroxylated carbon nitride material CN-OH is added with a compound containing nickel or a nickel-loaded hydroxylated carbon nitride-based material Ni / CN-OH, halogenated aromatic hydrocarbons, and an inorganic base, which are dissolved in water or a mixture of water and a solvent, and reacted under light conditions to obtain a phenol compound; or, the photocatalyst hydroxylated carbon nitride material CN-OH is added with a compound containing nickel or a nickel-loaded hydroxylated carbon nitride-based material Ni / CN-OH, halogenated aromatic hydrocarbons, an inorganic base and an alcohol substance or a solvent containing an alcohol substance, and reacted under light conditions to obtain an aromatic ether compound.

[0054] According to an embodiment of the present invention, the reaction can be carried out in a light-transmitting photoreactor. The photoreactor needs to be sealed and deoxygenated to obtain better reaction activity. The reaction can also be carried out without deoxygenation, but the efficiency will be reduced.

[0055] According to an embodiment of the present invention, the illumination condition may be blue light irradiation with a wavelength ranging from 400 to 550 nm, preferably 420 nm.

[0056] According to an embodiment of the present invention, the inorganic base is selected from one of NaOH, KOH, LiOH, Ca(OH)2, K2CO3, and Na2CO3, preferably NaOH, and the molar ratio of the inorganic base to the substrate halogenated aromatic hydrocarbon is 1 to 5:1, exemplified as 2:1.

[0057] According to an embodiment of the present invention, the concentration of the photocatalyst CN-OH or Ni / CN-OH in the reaction system is 0.1-5 g / L, for example, 0.1 g / L, 0.5 g / L, 1 g / L, 2 g / L, 5 g / L, preferably 2 g / L.

[0058] According to an embodiment of the present invention, the concentration of the halogenated aromatic hydrocarbon in the reaction system is 0.001-1 mol / L, for example 0.02 mol / L.

[0059] According to an embodiment of the present invention, the solvent in the mixture of water and solvent, or the solvent in the solvent containing alcohol substance is the same or different, and is independently selected from: pure water, alcohol, or a mixed solvent of water and an organic solvent, a mixed solvent of alcohol and an organic solvent, and the organic solvent can be 1,4-dioxane, an amide solvent (such as N,N dimethylformamide, N,N dimethylacetamide), acetonitrile, etc., and the volume ratio of water or alcohol to organic solvent in the mixed solvent is 1:9 to 9:1, for example, 1:1.

[0060] According to an embodiment of the present invention, the reaction temperature may be above 0°C, for example, 10-45°C, such as 40°C; the reaction time may be above 1h, for example, 6h, 8h, 10h, 12h.

[0061] According to an embodiment of the present invention, the reaction is carried out under stirring.

[0062] Beneficial Effects

[0063] (1) The present invention provides a catalyst composition comprising a hydroxylated carbon nitride material and a compound containing a nickel element, wherein the composition is used as a photocatalyst in a visible light catalytic cross-coupling reaction of a halogenated aromatic hydrocarbon substrate with water / alcohol to obtain a phenolic compound or an aromatic ether compound. The composition can efficiently realize the coupling of an electron-deficient halogenated aromatic hydrocarbon with water or alcohol under mild conditions, the reaction conditions are green and mild, and the system and operation are simple.

[0064] (2) The hydroxylated carbon nitride material and the nickel-containing compound can be added to the system separately, or the nickel-containing compound can be loaded onto the hydroxylated carbon nitride material. By adjusting the mass ratio of the hydroxylated carbon nitride to the nickel-containing compound, carbon nitride-based nickel-containing materials with different loading amounts, i.e., Ni / CN-OH, can be obtained. The synthesis conditions of Ni / CN-OH are mild and easy to operate.

[0065] (3) The hydroxylated carbon nitride material of the present invention is prepared by a hydrothermal synthesis method, and the preparation method has high repeatability. Through microwave assistance, the hydroxylated carbon nitride can effectively and more frequently anchor metal sites to form highly dispersed active sites, thereby improving its photocatalytic activity.

[0066] (4) The present invention can realize the cross-coupling reaction of water and halogenated aromatic hydrocarbons in a variety of solvents. By selecting a suitable polar solvent, it is beneficial to the efficient conversion of different substrates to phenols; at the same time, it can also efficiently realize the carbon-oxygen cross-coupling reaction of alcohols and halogenated aromatic hydrocarbons to ethers.

[0067] (5) The preparation method of the hydroxylated carbon nitride material of the present invention has mild conditions and low raw material cost. The catalytic scheme has good application prospects in the fields of photocatalytic green organic synthesis and environmental remediation.

[0068] Terms and Definitions

[0069] The term "C 1-12 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably C 1-10 Alkyl. "C 1-10“Alkyl” is understood as meaning a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl radical is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers. In particular, the radical has 1, 2, 3, 4, 5 or 6 carbon atoms (“C 1-6 alkyl), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly, the radical having 1, 2 or 3 carbon atoms (“C 1-3 "alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0070] The term "C 1-12 "Alkoxy" means "-OC 1-12 Alkyl", where C 1-12 Alkyl has the same meaning as defined above.

[0071] The term "halogenated C 1-12 Alkyl", "-COC 1-12 Alkyl" and "-COOC 1-12 C in "alkyl" 1-12 Alkyl has the same meaning as defined above.

[0072] The term "C 3-20 "Cycloalkyl" should be understood to mean a saturated monocyclic, bicyclic or polycyclic hydrocarbon ring (also called condensed hydrocarbon ring) having 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyls include paracyclic cycloalkyls, bridged cycloalkyls and spirocyclic cycloalkyls; the paracyclic refers to a condensed ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. The spirocyclic refers to a condensed ring structure formed by two or more cyclic structures sharing one ring atom. For example, the C 3-20 The cycloalkyl group may be C 3-8 Monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Cycloalkyl ring, such as decalin ring.

[0073] The term "3-20 membered heterocyclyl" means a saturated monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O and S, preferably a "3-12 membered heterocyclyl". The term "3-12 membered heterocyclyl" means a saturated monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl may be connected to the rest of the molecule through any one of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclyl may include, but is not limited to: a 4-membered ring, such as azetidinyl, oxetanyl; a 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring, such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazine-2(1H)-yl ring. The ring containing the nitrogen atom may be partially unsaturated, i.e., it may contain one or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl.

[0074] The term "C 6-20 "Aryl" is understood to mean an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C 6-14 "Aryl" is understood to mean preferably an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 "aryl"), for example anthracenyl.

[0075] The term "5-20 membered heteroaryl" is understood to include mono-, bi- or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-12 membered heteroaryl". The term "5-12 membered heteroaryl" is understood to include mono-, bi- or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like.

[0076] The term "C 6-20 "Aromatic hydrocarbon" is understood to mean an aromatic or partially aromatic monocyclic, bicyclic, tricyclic or more cyclic hydrocarbon ring having 6 to 20 carbon atoms. Preferably, "C 6-14 Aromatic hydrocarbons", the term "C 6-14 The term "aromatic hydrocarbon" is understood to mean preferably an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 C6 aromatics), in particular rings with 6 carbon atoms ("C6 aromatics"), such as benzene or biphenyl, or rings with 9 carbon atoms ("C9 aromatics"), such as indane or indene, or rings with 10 carbon atoms ("C 10 Aromatic hydrocarbons”), such as tetralin, dilin or naphthalene, or rings having 13 carbon atoms (“C 13 Aromatic hydrocarbons”), such as fluorene, or rings with 14 carbon atoms (“C 14The term "5-20 membered heteroaromatic hydrocarbon" is understood to include monocyclic, bicyclic, tricyclic aromatic ring systems or more aromatic ring systems: it has 5 to 20 ring atoms and contains 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaromatic hydrocarbon". The term "5-14 membered heteroaromatic hydrocarbon" is understood to include monocyclic, bicyclic or tricyclic aromatic ring systems: it has 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and it contains 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S, and in each case may additionally be benzene. and fused. In particular, the heteroaromatic hydrocarbon is selected from thiophene, furan, pyrrole, oxazole, thiazole, imidazole, pyrazole, isoxazole, isothiazole, oxadiazole, triazole, thiadiazole, thia-4H-pyrazole, etc. and their benzo derivatives, such as benzofuran, benzothiophene, benzoxazole, benzisoxazole, benzimidazole, benzotriazole, indazole, indole, isoindole, etc.; or pyridine, pyridazine, pyrimidine, pyrazine, triazine, etc., and their benzo derivatives, such as quinoline, quinazoline, isoquinoline, etc.; or azine, indolizine, purine, etc. and their benzo derivatives; or cinnoline, phthalazine, quinazoline, quinoxaline, naphthyridine, pteridine, carbazole, acridine, phenazine, phenothiazine, phenoxazine, etc.

[0077] Unless otherwise stated, a heteroarene or heteroarene includes all possible isomeric forms thereof, such as positional isomers thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 1 is a Fourier transform infrared spectra of ordinary carbon nitride (CN) and hydroxylated carbon nitride (CN-OH) prepared in Example 1.

[0079] Figure 2 1 is the X-ray absorption spectrum of C1s and O1s of ordinary carbon nitride (CN) and hydroxylated carbon nitride (CN-OH) prepared in Example 1.

[0080] Figure 3 This is the HPLC spectrum obtained after the reaction of p-bromobenzonitrile with water for 6 hours in Application Example 1. DETAILED DESCRIPTION

[0081] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0082] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0083] In the following examples of the present invention, an Agilent HPLC 1260 liquid chromatograph equipped with a Dikma Diamonsil C-18 chromatographic column (250×3.0 mm, 5-μm film thickness) was used to quantitatively determine the yield of the reaction product using a calibration curve of a material standard.

[0084] Example 1

[0085] The preparation method of surface hydroxylated carbon nitride, i.e. hydroxylated carbon nitride material (CN-OH) is as follows:

[0086] Weigh 20g of urea in four 50mL crucibles, place them in a Thermo Fisher muffle furnace, heat to 550℃ at a heating rate of 5℃ / min, maintain at 550℃ for 4h, and then cool naturally to room temperature. Take out the ordinary yellow carbon nitride (CN) generated by the reaction and grind it evenly. Weigh 500mg of ordinary carbon nitride in a beaker, add 50mL of deionized water, and stir for 1h to form a suspension. Put the mixed solution into a hydrothermal reactor, then put the reactor into an oven, heat to 160℃ for 35min, maintain at 160℃ for 10h, cool to room temperature in 1.5h, filter the cooled reaction solution and wash it with ethanol and water at least twice respectively, put the obtained light yellow solid sample into a vacuum oven, and bake it at 80℃ for at least 4h to obtain surface hydroxylated carbon nitride (CN-OH).

[0087] Preparation of nickel-loaded hydroxylated carbon nitride material (Ni / CN-OH):

[0088] 100 mg of the surface hydroxylated carbon nitride (CN-OH) prepared above was dispersed in 7.5 mL of acetonitrile solution containing 5 mg NiCl2·6H2O, 65 μL of triethylamine was added, and the mixture was stirred for 1 h. The mixture was placed in an MCR-3 microwave reactor, microwaved at 80°C for two hours, naturally cooled to room temperature, filtered, washed twice with chloroform, methanol, and acetonitrile, and vacuum dried at 80°C for at least 2 h to obtain a light yellow solid, that is, a nickel-loaded hydroxylated carbon nitride material (Ni / CN-OH) was obtained.

[0089] The Fourier transform infrared spectra and X-ray absorption spectra of ordinary carbon nitride (CN) and surface hydroxylated carbon nitride (CN-OH) are shown in Figure 2. Figure 1 and Figure 2 As shown, it is confirmed that the surface hydroxylated carbon nitride has significantly increased hydroxyl groups.

[0090] Application Example 1

[0091] The photocatalytic carbon-oxygen cross-coupling reaction of halogenated aromatics with water to produce phenols is as follows:

[0092] 10 mg of Ni / CN-OH prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH and 5 mL of pure water were added to the photoreactor. Then, argon or nitrogen was blown for 15 minutes for deoxygenation under magnetic stirring. The photocatalytic reaction was carried out under the irradiation of a multi-channel photoreactor equipped with a 420 nm LED lamp. The reaction temperature was maintained at 40° C. with circulating condensed water. After 6 hours of reaction, the product p-cyanophenol was obtained. The HPLC spectra of the reaction product p-cyanophenol and the incompletely reacted substrate are shown in FIG. Figure 3 As shown (the yield of phenol in 6h was 70%). Figure 3 It shows that after adding photocatalyst to the pure water system containing inorganic base, the system can realize the conversion of halogenated aromatics into phenols under 420nm LED irradiation.

[0093] Application Example 2

[0094] The photocatalytic carbon-oxygen cross-coupling reaction of halogenated aromatics with water to produce phenols is as follows:

[0095] 10 mg of CN-OH prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH, 0.01 mmol of NiCl2·6H2O and 5 mL of pure water were added to a photoreactor. Then, argon or nitrogen was blown for 15 minutes for deoxygenation under magnetic stirring. The photocatalytic reaction was carried out under the irradiation of a multi-channel photoreactor equipped with a 420 nm LED lamp. The reaction temperature was maintained at 40° C. with circulating condensed water. After 6 h of reaction, the product p-cyanophenol was obtained with a yield of 44%.

[0096] Application Example 3

[0097] The photocatalytic carbon-oxygen cross-coupling reaction of halogenated aromatics with water to produce phenols is as follows:

[0098] 10 mg of CN-OH prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH, 0.01 mmol of NiCl2·6H2O, 2.5 mL of pure water and 2.5 mL of 1,4-dioxane were added to the photoreactor. Then, argon or nitrogen was blown for 15 minutes for deoxygenation under magnetic stirring. The photocatalytic reaction was carried out under the irradiation of a multi-channel photoreactor equipped with a 420 nm LED lamp. The reaction temperature was maintained at 40°C with circulating condensed water. After 6 hours of reaction, the product p-cyanophenol was obtained with a yield of 60% (when the reaction time was extended to 12 hours, the yield was 85%).

[0099] Application Examples 4-6

[0100] By replacing the 1,4-dioxane in Application Example 3 with acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide, p-cyanophenol can be obtained, and the product yields are 50%, 44%, and 45%, respectively.

[0101] Application Example 7

[0102] Photocatalytic carbon-oxygen cross-coupling reaction of halogenated aromatics with methanol to produce ethers

[0103] The water in Application Example 2 was replaced with methanol to obtain p-cyanoanisole with a product yield of 71%.

[0104] Comparative application example 1

[0105] 10 mg of CN-OH prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH, 0.01 mmol of NiCl2·6H2O and 5 mL of pure water were added to the photoreactor. Then, argon or nitrogen was blown for 15 minutes under magnetic stirring to deoxygenate. The reaction temperature was maintained at 40°C with circulating condensed water. After 6 hours of reaction without light, no p-cyanophenol was generated.

[0106] Comparative Application Example 2

[0107] 10 mg of CN-OH prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH and 5 mL of pure water were added to a photoreactor. Then, argon or nitrogen was blown for 15 minutes for deoxygenation under magnetic stirring. The photocatalytic reaction was carried out under the irradiation of a multi-channel photoreactor equipped with a 420 nm LED lamp. The reaction temperature was maintained at 40° C. with circulating condensed water. After 6 hours of reaction, no p-cyanophenol was generated.

[0108] Comparative Application Example 3

[0109] 10 mg of CN (normal carbon nitride) prepared in Example 1, 0.1 mmol of p-bromobenzonitrile, 0.2 mmol of NaOH, 0.01 mmol of NiCl2·6H2O, 2.5 mL of pure water and 2.5 mL of 1,4-dioxane were added to the photoreactor. Then, argon or nitrogen was blown for 15 minutes for deoxygenation under magnetic stirring. The photocatalytic reaction was carried out under the irradiation of a multi-channel photoreactor equipped with a 420 nm LED lamp. The reaction temperature was maintained at 40° C. with circulating condensed water. After 6 hours of reaction, the product p-cyanophenol was obtained in a yield of 3%.

[0110] The above is a description of the exemplary embodiments of the present invention. However, the protection scope of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A catalyst composition, characterized in that The composition comprises: a hydroxylated carbon nitride material and a compound containing nickel element.

2. The catalyst composition according to claim 1, wherein The catalyst composition is used for photocatalytic reaction of halogenated aromatic hydrocarbons with water to generate phenolic compounds or for photocatalytic reaction of halogenated aromatic hydrocarbons with alcohol substances to generate aromatic ether compounds; Preferably, the molar ratio of the nickel-containing compound to the substrate halogenated aromatic hydrocarbon is 1:(5-1000); Preferably, the reaction to generate a phenolic compound or the reaction to generate an aromatic ether compound is carried out in the presence of a base; Preferably, the base is an inorganic base or an organic base; Preferably, the molar ratio of the base to the halogenated aromatic hydrocarbon is (1-50):1; Preferably, the halogenated aromatic hydrocarbon is an iodinated aromatic hydrocarbon, a brominated aromatic hydrocarbon or a chlorinated aromatic hydrocarbon; Preferably, the aromatic hydrocarbon is selected from C 6-20 Aromatic hydrocarbons or 5-20 membered heteroaromatic hydrocarbons; Preferably, the C 6-20 The aromatic hydrocarbon or 5-20 membered heteroaromatic hydrocarbon is optionally substituted by one, two or more groups Rs which are inert to the photocatalytic reaction, wherein Rs is selected from the following groups: CN, CHO, C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC 1-12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl; The C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 The aryl or 5-20 membered heteroaryl group is further optionally substituted by one, two or more groups Ra which are inert to the photocatalytic reaction; The Ra is selected from the following groups: CN, CHO, C 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, -COC 1-12 Alkyl or -COOC 1-12 alkyl.

3. The catalyst composition according to claim 2, wherein The number of halide ions iodine, bromine or chlorine in the iodinated aromatic hydrocarbon, brominated aromatic hydrocarbon or chloroaromatic hydrocarbon is at least 1; Preferably, the alcohol substance is a monohydric alcohol having a carbon number less than 10, for example, at least one of methanol, ethanol, propanol and n-butanol.

4. The catalyst composition according to any one of claims 1 to 3, wherein The halogenated aromatic hydrocarbon is at least one of iodobenzene, bromobenzene, chlorobenzene, p-iodoacetophenone, p-bromoacetophenone, p-chloroacetophenone, p-iodobenzonitrile, p-bromobenzonitrile, p-chlorobenzonitrile, p-iodobenzotrifluoride, p-bromobenzotrifluoride, p-iodobenzaldehyde, p-bromobenzaldehyde, p-chlorobenzaldehyde, methyl p-bromobenzoate, and m-bromoacetophenone.

5. The catalyst composition according to any one of claims 1 to 4, wherein The nickel-containing compound is selected from one, two or more of nickel sulfate, nickel bromide, nickel acetate, nickel nitrate, nickel chloride, nickel acetylacetonate, nickel perchlorate and hydrates thereof; Preferably, the mass ratio of the compound containing nickel element to the hydroxylated carbon nitride material is 1:(10-2000).

6. Use of the catalyst composition according to any one of claims 1 to 5 for photocatalytic reaction of halogenated aromatic hydrocarbons with water to generate phenolic compounds, or for photocatalytic reaction of halogenated aromatic hydrocarbons with alcohols to generate aromatic ether compounds.

7. A method for preparing a phenolic compound or an aromatic ether compound, wherein: The method comprises the following steps: subjecting halogenated aromatic hydrocarbons and water or alcohol substances to a light irradiation reaction in the presence of any one of the catalyst compositions of claims 1-5.

8. The preparation method according to claim 7, wherein: The photoirradiation reaction is carried out under an inert gas atmosphere.

9. The preparation method according to claim 7 or 8, wherein: The molar ratio of the compound containing nickel element to the substrate halogenated aromatic hydrocarbon is 1:(5-1000); Preferably, the photoreaction is carried out in the presence of a base, such as an inorganic base or an organic base; Preferably, the inorganic base is selected from one of NaOH, KOH, LiOH, Ca(OH)2, K2CO3, and Na2CO3; Preferably, the molar ratio of the base to the halogenated aromatic hydrocarbon is (1-50):

1.

10. The preparation method according to any one of claims 7 to 9, wherein: The light irradiation reaction uses blue light irradiation with a wavelength range of 400 to 550 nm.

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