Application of carbon nitride-based copper monatomic photocatalyst in hydrophosphonylation reaction

Abstract

The application provides application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction and belongs to the technical field of catalytic materials. The copper monatomic photocatalyst is used to form a Cu-N4 coordination structure by coordination of copper monatomic and nitrogen on the carbon nitride carrier, so that the copper monatomic center can be stabilized and aggregation in the reaction can be avoided. The carbon nitride itself is an organic semiconductor material, can absorb light of a specific wavelength, realize charge separation, and can transmit electrons on a conduction band to a copper center and transmit holes to obtain electrons from a substrate. The catalyst can be used to catalyze phosphine hydrogenation reactions of olefins and acetylenes containing different functional groups, and excellent yields can be obtained. The catalyst is efficient and stable, and can maintain high catalytic efficiency after multiple cycles at room temperature and under light.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of catalytic materials, and in particular to application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction. BACKGROUND

[0002] The phosphine hydrogenation reaction refers to a reaction process in which a compound containing a P-H bond is added to an unsaturated carbon-carbon double bond or triple bond to construct a C-P bond. The atomic utilization rate of the reaction is 100%, and a phosphorus-containing functional group can be introduced in one step, which is an effective way to synthesize phosphorus-containing compounds. Phosphorus-containing compounds have unique drug activity, and have been widely concerned in the fields of medicine, pesticides and the like. For example, phosphorus-containing compounds exist in anti-depression, anti-AIDS, anti-malaria, anti-influenza and other drugs. Meanwhile, phosphorus-containing compounds can also be used as ligands of metal complexes to regulate the activity and stability of metal catalysts.

[0003] Since the end of the last century, along with the rapid development of metal organic chemistry, the transition metal-catalyzed phosphine hydrogenation reaction has developed rapidly. Compared with the traditional method of synthesizing phosphorus compounds, the transition metal catalysis has the advantages of high atom economy, high selectivity and wide substrate applicability. However, the homogeneous transition metal catalytic system (especially the palladium and rhodium catalytic system) still has the challenges of difficult recovery and separation of the catalyst, high reaction temperature and the like, which increases the synthesis cost and carbon emission. In recent years, scientists have also explored the realization of the phosphine hydrogenation reaction under the condition of free radicals, and the cost is controlled compared with the transition metal catalytic system, but the reaction efficiency still needs to be improved. For the phosphine hydrogenation reaction, the reaction efficiency of the homogeneous catalytic strategy still needs to be improved, and few reaction systems can simultaneously accommodate carbon-carbon double bonds and carbon-carbon triple bonds, which may be related to the reaction mechanism. These limitations limit the large-scale industrial application of the phosphine hydrogenation reaction. SUMMARY

[0004] The application aims to provide application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction. The carbon nitride-based copper monatomic photocatalyst is used as a catalyst, and can catalyze the phosphine hydrogenation reaction of olefins and alkynes containing different functional groups, and excellent yield can be obtained. The reaction condition is mild, only room temperature and light are needed, the reaction is efficient, no additional additives are needed, and the reaction can be scaled up to a kilogram scale. The carbon nitride-based copper monatomic photocatalyst has good stability, can be recycled and reused, and can still maintain high catalytic efficiency after multiple cycles.

[0005] In order to achieve the above application purposes, the application provides the following technical solutions.

[0006] The application provides application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction,

[0007] Under light conditions, a carbon nitride-based copper monatomic photocatalyst is used as a catalyst to catalyze a phosphine hydrogen compound and an unsaturated hydrocarbon to perform a phosphine hydrogen addition reaction, so as to obtain a phosphorus-containing compound;

[0008] The carbon nitride-based copper monatomic photocatalyst is composed of a carbon nitride carrier and copper in a monatomic form, wherein the loading amount of copper in the carbon nitride-based copper monatomic photocatalyst is 0.1wt.% to 10wt.%.

[0009] The unsaturated hydrocarbon is an unsaturated olefin and / or an unsaturated alkyne.

[0010] Preferably, the light conditions are one or more of monochromatic LED light, full-spectrum xenon lamp light, sunlight and laser light.

[0011] Preferably, the light wavelength range of the light conditions is 254nm to 800nm, and the light intensity of the light conditions is 1000mW / cm 2 .

[0012] Preferably, the molar ratio of the phosphine hydrogen compound to the unsaturated hydrocarbon is (0.5 to 10):1.

[0013] Preferably, the molar ratio of the unsaturated hydrocarbon to the copper element in the carbon nitride-based copper monatomic photocatalyst is (50 to 2×10 7 ):1.

[0014] Preferably, the phosphine hydrogen compound has a structure shown in Formula I, Formula II, Formula III or Formula IV, or is limonene / norbornene;

[0015]

[0016] In the Formula I, II, III and IV, n=0 to 20, and m=0 to 20.

[0017] In the Formula I, II, III and IV, R 1 and R 2 are each independently selected from one of H, CH3, t Bu, OMe, NH2, OH, F, Cl, Br and I.

[0018] Preferably, the unsaturated olefin has a structure shown in Formula A1, Formula A2, Formula A3 or Formula A4:

[0019]

[0020] In the Formula A1, A2, A3 and A4, n=0 to 20, m=0 to 20, o=0 to 20, and p=0 to 20, and R 1 , R2 R 3 and R 4 are each independently selected from H, CH3, t Bu, OMe, NH2, OH, F, Cl, Br and I.

[0021] Preferably, the unsaturated alkyne has a structure represented by Formula B1 or Formula B2, or is norethindrone;

[0022]

[0023] n = 0-20 and m = 0-20 in the Formula B1 and Formula B2;

[0024] R 1 and R 2 are each independently selected from H, CH3, t Bu, OMe, NH2, OH, F, Cl, Br and I.

[0025] Preferably, the carbon nitride-based copper monatomic photocatalyst can be recycled and used in intermittent batch reactions.

[0026] Preferably, the preparation method of the carbon nitride-based copper monatomic photocatalyst is one or more of impregnation, precipitation, photoreduction, hydrothermal synthesis, and freeze-drying.

[0027] The application provides an application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction, and the carbon nitride-based copper monatomic photocatalyst is used as a catalyst to catalyze phosphine hydrogen compounds and unsaturated hydrocarbons to perform phosphine hydrogen addition reaction under light conditions, so as to obtain phosphorus-containing compounds; the carbon nitride-based copper monatomic photocatalyst is composed of a carbon nitride carrier and copper in a monatomic form, and the loading amount of copper in the carbon nitride-based copper monatomic photocatalyst is 0.1wt.%-10wt.%; the unsaturated hydrocarbon is unsaturated olefin and / or unsaturated alkyne. The carbon nitride-based copper monatomic photocatalyst is used to catalyze a series of unsaturated hydrocarbons to perform phosphine hydrogenation reaction under light conditions, the copper monatomic in the carbon nitride-based copper monatomic photocatalyst forms coordination with nitrogen on the carbon nitride carrier to form a Cu-N4 coordination structure, so as to stabilize the copper monatomic center and avoid aggregation in the reaction, and the carbon nitride itself is an organic semiconductor material, can absorb light of a specific wavelength, realize charge separation, the electrons on the conduction band can be transmitted to the copper center, and the holes can obtain electrons from the substrate, so as to promote the occurrence of the phosphine hydrogenation reaction. The carbon nitride-based copper monatomic photocatalyst in the application can catalyze olefins and alkyne containing different functional groups, and excellent yield can be obtained. There is rarely report on homogeneous catalytic system, and the reaction condition is mild, only needs room temperature and light, the reaction is efficient, no additional additives are needed, and the reaction can be realized on a kilogram scale. Moreover, the stability of the carbon nitride-based copper monatomic photocatalyst is good, and the carbon nitride-based copper monatomic photocatalyst can be recovered and reused after simple suction filtration, washing and drying, and can still maintain high catalytic efficiency after multiple cycles. DETAILED DESCRIPTION

[0028] The application provides an application of a carbon nitride-based copper monatomic photocatalyst in a phosphine hydrogenation reaction,

[0029] The carbon nitride-based copper monatomic photocatalyst is used as a catalyst to catalyze phosphine hydrogen compounds and unsaturated hydrocarbons to perform phosphine hydrogen addition reaction under light conditions, so as to obtain phosphorus-containing compounds.

[0030] The carbon nitride-based copper monatomic photocatalyst is composed of a carbon nitride carrier and copper in a monatomic form, and the loading amount of copper in the carbon nitride-based copper monatomic photocatalyst is 0.1wt.%-10wt.%.

[0031] The unsaturated hydrocarbon is unsaturated olefin and / or unsaturated alkyne.

[0032] In the application, if no special description is given, the raw materials used are all conventional commercially available products in the field.

[0033] In the application, the preparation method of the carbon nitride-based copper monatomic photocatalyst is preferably one or more of impregnation, precipitation, photoreduction, hydrothermal synthesis and freeze-drying.

[0034] In the present application, the method for preparing a carbon nitride-based copper monatomic photocatalyst by photoreduction comprises the following steps:

[0035] (1) Carbon nitride / carbon nitride derivative and copper complex (CuLnXm) are added into an organic solvent in a mass ratio of (20-1000):1 (copper complex is calculated based on the mass of copper metal), and a dispersion liquid is obtained by stirring or ultrasonic treatment;

[0036] The copper complex CuL n X m The organic ligand L in the copper complex is one or more of bipyridine (bpy), p-tert-butyl bipyridine (dtbbpy), triphenylphosphine (PPh3), acetylacetone (acac), phenanthroline (phen), benzoylacetone (bac), and oct-1,5-diene (cod), n is 1-4, X is one of Cl, Br, and F, and m is 0-3.

[0037] (2) The organic solvent in the dispersion liquid obtained in step (1) is removed under the conditions of a temperature of 0-150°C and / or reduced pressure to obtain a copper complex precursor and a carbon nitride / carbon nitride derivative mixed solid;

[0038] (3) The copper complex precursor and the carbon nitride / carbon nitride derivative mixed solid obtained in step (2) are mixed with water, and then irradiated under the condition of light with a wavelength range of 254-800 nm for 1-600 min to obtain a mixture; the concentration of the copper complex precursor and the carbon nitride / carbon nitride derivative mixed solid in the mixture ranges from 0.1 to 100 mg / mL;

[0039] (4) The mixture obtained in step (3) is filtered or centrifuged to obtain a light-irradiated solid, which is then dried or calcined at a temperature of 50-500°C to obtain a dried solid;

[0040] (5) The dried solid obtained in step (4) is washed with an organic solvent to remove unreacted copper complex, and then dried again to obtain a carbon nitride-based copper monatomic photocatalyst.

[0041] The carbon nitride-based copper monatomic photocatalyst in the present application has a conjugated and coordinated structure, which accelerates the transmission efficiency of electrons, and the low-valence copper atom center is stabilized by nitrogen coordination, so that it is not easy to aggregate, thereby prolonging the life and obtaining excellent cycle stability.

[0042] In the present application, the solvent used in the phosphine hydrogenation reaction is preferably N,N-dimethylformamide. In the present application, the atmosphere of the phosphine hydrogenation reaction is preferably argon.

[0043] In this invention, the illumination conditions are preferably one or more of monochrome LED illumination, full-spectrum xenon lamp illumination, sunlight illumination, and laser illumination.

[0044] In this invention, the wavelength range of the illumination conditions is preferably 254–800 nm, more preferably 365–500 nm. In this invention, the light intensity of the illumination conditions is preferably 1000–12000 mW / cm². 2 In this invention, the preferred temperature for the illumination conditions is -20 to 100°C.

[0045] In this invention, the molar ratio of the phosphine hydride to the unsaturated hydrocarbon is preferably (0.5–10):1, more preferably (1–8):1. This invention controls the molar ratio of the phosphine hydride to the unsaturated hydrocarbon within the above range to obtain phosphorus-containing compounds with higher yields and selectivity.

[0046] In this invention, the molar ratio of the unsaturated hydrocarbon to the copper element in the carbon nitride-based copper single-atom photocatalyst is (50~2×10). 7 ): 1, more preferably (80~1×10 7 ): 10. The present invention controls the molar ratio of unsaturated hydrocarbons to copper in carbon nitride-based copper single-atom photocatalysts within the above-mentioned range to obtain phosphorus-containing compounds with higher yield and selectivity.

[0047] In this invention, the phosphine compound preferably has the structure shown in Formula I, Formula II, Formula III or Formula IV, or is limonene / norbornene;

[0048]

[0049] In this invention, n = 0 to 20 and m = 0 to 20 in formulas I, II, III and IV.

[0050] In this invention, R in formulas I, II, III and IV 1 and R 2 H, CH3, and H are preferred independently. t Bu、OMe、 One of NH2, OH, F, Cl, Br and I.

[0051] In this invention, the unsaturated olefin preferably has the structure shown in formula A1, formula A2, formula A3 or formula A4;

[0052]

[0053] In this invention, n = 0 to 20, m = 0 to 20, o = 0 to 20, and p = 0 to 20 in formulas A1, A2, A3, and A4.

[0054] In the present application, R 1 , R 2 , R 3 and R 4 are each independently preferably H, CH3, t Bu, OMe, NH2, OH, F, Cl, Br and I.

[0055] In the present application, the unsaturated alkyne is preferably of formula B1 or formula B2, or is norethindrone;

[0056]

[0057] In the present application, n = 0-20 and m = 0-20 in formula B1 and formula B2.

[0058] In the present application, R 1 and R 2 are each independently selected from H, CH3, t Bu, OMe, NH2, OH, F, Cl, Br and I.

[0059] After completion of the hydrophosphonylation reaction, the present application preferably filters and separates the product of the hydrophosphonylation reaction to obtain recovered carbon nitride-based copper monatomic photocatalyst solids and a colorless solution containing the product.

[0060] The present application does not have special restrictions on the manner of filtering and separating, and solid-liquid separation can be achieved using a technical solution well known in the art.

[0061] In the present application, the carbon nitride-based copper monatomic photocatalyst or the recovered carbon nitride-based copper monatomic photocatalyst solids can be recycled and used in batch reactions.

[0062] After obtaining the colorless solution containing the product, the present application separates the colorless solution containing the product by column chromatography to obtain a phosphorus-containing compound product,

[0063] The present application does not have special restrictions on the manner of column chromatography separation, and separation of the phosphorus-containing compound can be achieved using a technical solution well known in the art.

[0064] The technical solutions in the present application will be clearly and completely described below in combination with the embodiments in the present application. Apparently, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort should fall within the protection scope of the present application.

[0065] Embodiment 1

[0066] The method for preparing the carbon nitride-based copper monatomic photocatalyst by using a hydrothermal synthesis method comprises the following steps:

[0067] (1) 50 g of urea is heated at 550 ℃ for 2 hours (2 ℃ / min temperature rise), and then kept for 2 hours, and the product is washed with pure water to obtain carbon nitride;

[0068] 200 mg of the carbon nitride is added to 20 mL of water, and ultrasonic treatment is performed for 60 min to obtain a uniform carbon nitride-water dispersion;

[0069] (2) 5 mL of a copper chloride aqueous solution (20 mg of copper chloride, 10 mL of water) is added dropwise into the carbon nitride-water dispersion obtained in the step (1) at a speed of 2 mL / h by using a syringe pump under stirring at room temperature, to obtain a mixture;

[0070] (3) The mixture obtained in the step (2) is heated to 100 ℃, and after refluxing for 2 hours, filtration and drying are performed, to obtain a light yellow solid powder, which is the carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-1, and the loading amount of copper in the Cu1 / CN-1 is 2.3 wt.% measured by ICP.

[0071] Embodiment 2

[0072] The method for preparing the carbon nitride-based copper monatomic photocatalyst by using a hydrothermal synthesis method comprises the following steps:

[0073] (1) 50 g of dicyandiamide is heated at 550 ℃ for 2 hours (5 ℃ / min temperature rise), and then kept for 2 hours, and the product is washed with pure water to obtain carbon nitride;

[0074] 200 mg of the carbon nitride is added to 20 mL of water, and ultrasonic treatment is performed for 60 min to obtain a uniform carbon nitride-water dispersion;

[0075] (2) 5 mL of a copper chloride aqueous solution (20 mg of copper chloride, 10 mL of water) is added dropwise into the carbon nitride-water dispersion obtained in the step (1) at a speed of 2 mL / h by using a syringe pump under stirring at room temperature, to obtain a mixture;

[0076] (3) The mixture obtained in step (2) was heated to 100°C and refluxed for 2 hours, and then filtered and dried to obtain a yellowish solid powder, which was a carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-2. The copper loading in Cu1 / CN-2 was 1.7 wt.% as measured by ICP.

[0077] Example 3

[0078] The method for preparing the carbon nitride-based copper monatomic photocatalyst by the freeze-drying method comprises the following steps:

[0079] (1) 50 g of urea was heated at 550°C for 2 hours (2°C / min heating), and then kept for 2 hours. The product was washed with pure water to obtain carbon nitride;

[0080] 200 mg of carbon nitride was added to 20 mL of water and ultrasonically treated for 60 min to obtain a uniform carbon nitride-water dispersion;

[0081] (2) 5 mL of copper chloride aqueous solution (20 mg of copper chloride, 10 mL of water) was added to the carbon nitride-water dispersion obtained in step (1) at a speed of 2 mL / h by a syringe pump under stirring at room temperature to obtain a mixture;

[0082] (3) The mixture obtained in step (2) was heated to 100°C and refluxed for 2 hours, and then filtered and dried to obtain a yellowish solid powder, which was a carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-2. The copper loading in Cu1 / CN-2 was 1.7 wt.% as measured by ICP.

[0083] Example 4

[0084] The method for preparing the carbon nitride-based copper monatomic photocatalyst by the freeze-drying method comprises the following steps:

[0085] (1) 50 g of urea was heated at 550°C for 2 hours (2°C / min heating), and then kept for 2 hours. The product was washed with pure water to obtain carbon nitride;

[0086] 200 mg of carbon nitride was added to 20 mL of water and ultrasonically treated for 60 min to obtain a uniform carbon nitride-water dispersion;

[0087] (2) 5 mL of copper chloride aqueous solution (20 mg of copper chloride, 10 mL of water) was added to the carbon nitride-water dispersion obtained in step (1) at a speed of 2 mL / h by a syringe pump under stirring at room temperature to obtain a mixture;

[0088] (3) The mixture obtained in step (2) was stirred at room temperature for 4 hours, and water was removed by using a freeze dryer to obtain a light yellow solid powder, which was a carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-4. The copper loading in Cu1 / CN-4 was 3.4 wt.%, as determined by ICP.

[0089] Example 5

[0090] The method for preparing the carbon nitride-based copper monatomic photocatalyst by the photoreduction method comprises the following steps:

[0091] (1) 50 g of urea was heated at 550°C for 2 hours (2°C / min temperature rise), and then kept for 2 hours. The product was washed with pure water to obtain carbon nitride;

[0092] 200 mg of carbon nitride was added to 20 mL of water and ultrasonically treated for 60 min to form a uniform carbon nitride-water dispersion;

[0093] (2) 5 mL of an aqueous copper chloride solution (20 mg of copper chloride, 10 mL of water) was added dropwise to the carbon nitride-water dispersion obtained in step (1) at a rate of 2 mL / h by using a syringe pump under stirring at room temperature to obtain a mixture;

[0094] (3) The mixture obtained in step (2) was stirred at room temperature for 4 hours, and water was removed by using a freeze dryer. Then, the mixture was irradiated with a xenon lamp for 2 hours to obtain a light yellow solid powder, which was a carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-5. The copper loading in Cu1 / CN-5 was 3.3 wt.%, as determined by ICP.

[0095] Example 6

[0096] The method for preparing the carbon nitride-based copper monatomic photocatalyst by the photoreduction method comprises the following steps:

[0097] (1) 50 g of urea was heated at 550°C for 2 hours (2°C / min temperature rise), and then kept for 2 hours. The product was washed with pure water to obtain carbon nitride;

[0098] 200 mg of carbon nitride was added to 20 mL of water and ultrasonically treated for 60 min to form a uniform carbon nitride-water dispersion;

[0099] (2) The carbon nitride-dichloromethane dispersion obtained in step (1) was stirred at room temperature for 4 hours, and then irradiated with a xenon lamp under vacuum for 3 hours. The mixture was sequentially subjected to suction filtration, washing and drying to obtain a light yellow solid powder, which was a carbon nitride-based copper monatomic photocatalyst, denoted as Cu1 / CN-6. The copper loading was 0.63 wt.%, as determined by ICP.

[0100] Application Example 1

[0101] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-1 prepared in Example 1 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0102] 10 mg of Cu1 / CN-1 was added to a 10 mL quartz reaction tube containing 1-octene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol), and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform a phosphine hydrogen addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphorus-containing compound product yield) in the phosphine hydrogen addition reaction was 97%;

[0103] The structural formula of the product is:

[0104] Application Example 2

[0105] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-1 prepared in Example 1 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0106] 20 mg of Cu1 / CN-1 was added to a 20 mL quartz reaction tube containing 1-octene (11 mmol), diphenyl phosphine oxide (10 mmol), and N,N-dimethylformamide (10 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 5 h to perform a phosphine hydrogen addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphorus-containing compound product yield) in the phosphine hydrogen addition reaction was 94%;

[0107] The structural formula of the phosphorus-containing compound product is:

[0108] Application Example 3

[0109] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-2 prepared in Example 2 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0110] Cu1 / CN-2 was added to a 10 mL quartz reaction tube containing n-butyl vinyl ether (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to carry out the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The phosphorus-containing compound product was obtained by column chromatography separation. The C-P bond formation reaction yield (i.e., the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 93%;

[0111] The structure of the phosphorus-containing compound product is as follows:

[0112] Application Example 4

[0113] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-3 prepared in Example 3 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0114] Cu1 / CN-3 was added to a 10 mL quartz reaction tube containing n-butyl acrylate (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to carry out the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The phosphorus-containing compound product was obtained by column chromatography separation. The C-P bond formation reaction yield (i.e., the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 83%;

[0115] The structure of the phosphorus-containing compound product is as follows:

[0116] Application Example 5

[0117] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-4 prepared in Example 4 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0118] Cu1 / CN-4 was added to a 10 mL quartz reaction tube containing 4-phenyl-1-butene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2The phosphorus hydroaddition reaction was carried out under light for 2 hours, and then the recovered carbon nitride-based copper single-atom photocatalyst solid and the colorless solution containing the product were obtained by filtration and separation. The phosphorus-containing compound product was obtained by column chromatography. The yield of the CP bonding reaction in the phosphorus hydroaddition reaction (i.e. the yield of the phosphorus-containing compound product) was 92%.

[0119] The structural formula of the phosphorus-containing compound product is:

[0120] Application Example 6

[0121] The carbon nitride-based copper single-atom photocatalyst Cu1 / CN-5 prepared in Example 5 was applied to the phosphine hydrogenation reaction, which consisted of the following steps:

[0122] 10 mg of Cu1 / CN-5 was added to a 10 mL quartz reaction tube containing 1-allylnaphthalene (1.1 mmol), diphenylphosphine oxide (1.0 mmol), and N,N-dimethylformamide (1 mL) as a solvent. The air in the tube was replaced with argon gas. The reaction tube was then irradiated with a monochromatic LED light (390 nm, 3000 mW / cm²). 2 The phosphorus hydroaddition reaction was carried out under light for 3 hours, and then the recovered carbon nitride-based copper single-atom photocatalyst solid and the colorless solution containing the product were obtained by filtration and separation. The phosphorus-containing compound product was obtained by column chromatography. The yield of the CP bonding reaction in the phosphorus hydroaddition reaction (i.e. the yield of the phosphorus-containing compound product) was 93%.

[0123] The structural formula of the phosphorus-containing compound product is:

[0124] Application Example 7

[0125] The carbon nitride-based copper single-atom photocatalyst Cu1 / CN-6 prepared in Example 6 was applied to the phosphine hydrogenation reaction, which consisted of the following steps:

[0126] 10 mg of Cu1 / CN-6 was added to 10 mL of a quartz reaction tube containing 1.1 mmol of 3-trimethylsilyl-1-propene, 1.0 mmol of diphenylphosphine oxide, and 1 mL of N,N-dimethylformamide as a solvent. The air in the tube was replaced with argon gas. The reaction tube was then irradiated with a monochromatic LED light (390 nm, 3000 mW / cm²). 2 The phosphorus hydroaddition reaction was carried out under light for 6 hours, and then the recovered carbon nitride-based copper single-atom photocatalyst solid and the colorless solution containing the product were obtained by filtration and separation. The phosphorus-containing compound product was obtained by column chromatography. The yield of the CP bonding reaction in the phosphorus hydroaddition reaction (i.e. the yield of the phosphorus-containing compound product) was 96%.

[0127] The structural formula of the phosphorus-containing compound product is as follows:

[0128] Application Example 8

[0129] The carbon nitride-based copper monatomic photocatalyst Cu1 / CN-1 prepared in Example 1 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0130] 10 mg of Cu1 / CN-1 was added to a 10 mL quartz reaction tube containing 5- carbonyl-1-hexene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N- dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform a phosphine hydrogen addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphorus-containing compound product yield) in the phosphine hydrogen addition reaction was 85%;

[0131] The structure of the phosphorus-containing compound product was:

[0132] Application Example 9

[0133] The catalyst Cu1 / CN-3 obtained in Example 3 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0134] 10 mg of Cu1 / CN-3 was added to a 10 mL quartz reaction tube containing 3-cyano-1- propene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 6 h to perform a phosphine hydrogen addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphorus-containing compound product yield) in the phosphine hydrogen addition reaction was 80%;

[0135] The structure of the phosphorus-containing compound product was:

[0136] Application Example 10

[0137] The catalyst Cu1 / CN-5 obtained in Example 5 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0138] Cu1 / CN-5 was added to a 10 mL quartz reaction tube containing 6-chloro-1-hexene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration, and the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e. the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 95%;

[0139] The structure of the phosphorus-containing compound product is:

[0140] Application Example 11

[0141] The catalyst Cu1 / CN-4 obtained in Example 4 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0142] Cu1 / CN-4 was added to a 10 mL quartz reaction tube containing 5-bromo-1-pentene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration, and the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e. the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 90%;

[0143] The structure of the phosphorus-containing compound product is:

[0144] Application Example 12

[0145] The catalyst Cu1 / CN-3 obtained in Example 3 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0146] Cu1 / CN-4 was added to a 10 mL quartz reaction tube containing 5-bromo-1-pentene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2) for 1 h, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The product was isolated by column chromatography. The C-P bond formation reaction yield (i.e., the product yield) in the phosphine hydrogenation addition reaction was 93%.

[0147] The product structure formula is as follows:

[0148] Application Example 13

[0149] The catalyst Cu1 / CN-6 obtained in Example 6 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0150] 10 mg of Cu1 / CN-6 was added to a quartz reaction tube containing 1 -octene (1.1 mmol), 4,4’-dimethyl diphenyl phosphine oxide (1.0 mmol), and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm2). The phosphine hydrogenation addition reaction was carried out for 1 h, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The product was isolated by column chromatography. The C-P bond formation reaction yield (i.e., the product yield) in the phosphine hydrogenation addition reaction was 96%. 2 ) for 1 h, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The product was isolated by column chromatography. The C-P bond formation reaction yield (i.e., the product yield) in the phosphine hydrogenation addition reaction was 93%.

[0151] The product structure formula is as follows:

[0152] Application Example 14

[0153] The catalyst Cu1 / CN-6 obtained in Example 6 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0154] 10 mg of Cu1 / CN-6 was added to a quartz reaction tube containing 1 -octene (1.1 mmol), 4,4’-dimethyl diphenyl phosphine oxide (1.0 mmol), and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm2). The phosphine hydrogenation addition reaction was carried out for 1 h, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The product was isolated by column chromatography. The C-P bond formation reaction yield (i.e., the product yield) in the phosphine hydrogenation addition reaction was 96%. 2 ) for 1 h, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration. The product was isolated by column chromatography. The C-P bond formation reaction yield (i.e., the product yield) in the phosphine hydrogenation addition reaction was 93%.

[0155] The product structure formula is as follows:

[0156] Application Example 15

[0157] The catalyst Cu1 / CN-6 obtained in Example 6 was applied to a hydrophosphonylation reaction, which consisted of the following steps:

[0158] 10 mg of Cu1 / CN-6 was added to a quartz reaction tube containing 10 mL of 1-octene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform a hydrophosphonylation reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphine compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphine compound product yield) in the hydrophosphonylation reaction was 99%;

[0159] The structure of the phosphine compound product is as follows:

[0160] Application Example 16

[0161] The catalyst Cu1 / CN-1 obtained in Example 1 was applied to a hydrophosphonylation reaction, which consisted of the following steps:

[0162] 10 mg of Cu1 / CN-1 was added to a quartz reaction tube containing 10 mL of 1-octene (1.1 mmol), 4,4’-di-tert-butyl diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform a hydrophosphonylation reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and a colorless solution containing the product were separated by filtration, the phosphine compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e., the phosphine compound product yield) in the hydrophosphonylation reaction was 99%;

[0163] The structure of the phosphine compound product is as follows:

[0164] Application Example 17

[0165] The catalyst Cu1 / CN-3 obtained in Example 3 was applied to a hydrophosphonylation reaction, which consisted of the following steps:

[0166] Cu1 / CN-3 was added to a 10 mL quartz reaction tube containing 1-hexyne (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration, and the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e. the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 86%;

[0167] The structure of the phosphorus-containing compound product is:

[0168] Application Example 18

[0169] The catalyst Cu1 / CN-6 obtained in Example 6 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0170] Cu1 / CN-6 was added to a 10 mL quartz reaction tube containing cyclohexylethylene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) for 1 h to perform the phosphine hydrogenation addition reaction, and then the recovered carbon nitride-based copper monatomic photocatalyst solid and the colorless solution containing the product were separated by filtration, and the phosphorus-containing compound product was separated by column chromatography, and the C-P bond formation reaction yield (i.e. the yield of the phosphorus-containing compound product) in the phosphine hydrogenation addition reaction was 77%;

[0171] The structure of the phosphorus-containing compound product is:

[0172] Application Example 19

[0173] The catalyst Cu1 / CN-3 obtained in Example 3 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0174] Cu1 / CN-3 was added to a 10 mL quartz reaction tube containing phenylacetylene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2) and the recovered carbon nitride-based copper monatomic photocatalyst solid was obtained by filtration separation, and a colorless solution containing the product was obtained, and the phosphine-containing compound product was obtained by column chromatography separation, and the C-P bond formation reaction yield (i.e. the phosphine-containing compound product yield) in the phosphine hydrogenation addition reaction was 55%;

[0175] The structure of the phosphine-containing compound product is as follows:

[0176] Application Example 20

[0177] The catalyst Cu1 / CN-3 obtained in Example 3 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0178] 10 mg of Cu1 / CN-3 was added to a quartz reaction tube containing 10 mL of 3-ethynylthiophene (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) and the recovered carbon nitride-based copper monatomic photocatalyst solid was obtained by filtration separation, and a colorless solution containing the product was obtained, and the phosphine-containing compound product was obtained by column chromatography separation, and the C-P bond formation reaction yield (i.e. the phosphine-containing compound product yield) in the phosphine hydrogenation addition reaction was 48%;

[0179] The structure of the phosphine-containing compound product is as follows:

[0180] Application Example 21

[0181] The catalyst Cu1 / CN-6 obtained in Example 6 was applied to a phosphine hydrogenation reaction, which consisted of the following steps:

[0182] 10 mg of Cu1 / CN-6 was added to a quartz reaction tube containing 10 mL of norethisterone (1.1 mmol), diphenyl phosphine oxide (1.0 mmol) and N,N-dimethylformamide (1 mL) as a solvent, the air in the reaction tube was replaced with argon, and the reaction tube was irradiated with monochromatic LED light (390 nm, 3000 mW / cm 2 ) and the recovered carbon nitride-based copper monatomic photocatalyst solid was obtained by filtration separation, and a colorless solution containing the product was obtained, and the phosphine-containing compound product was obtained by column chromatography separation, and the C-P bond formation reaction yield (i.e. the phosphine-containing compound product yield) in the phosphine hydrogenation addition reaction was 36%;

[0183] The structure of the phosphine-containing compound product is as follows: As can be known from the above, the present application uses carbon nitride-based copper monatomic photocatalyst as a catalyst to catalyze the phosphine hydrogen addition reaction, so that the C-P bond reaction yield (i.e. the yield of phosphorus-containing compound product) in the phosphine hydrogen addition reaction can reach 99%. The present application uses carbon nitride-based copper monatomic photocatalyst as a catalyst to catalyze the phosphine hydrogenation reaction of alkenes and alkynes containing different functional groups, and excellent yield can be obtained. The reaction condition is mild, only room temperature and light are needed, the reaction is efficient, no additional additives are needed, and gram-scale amplification can also be realized. The stability of the carbon nitride-based copper monatomic photocatalyst is good, and it can be recycled and reused, and can still maintain high catalytic efficiency after multiple cycles.

[0184] The above only describes the preferred embodiments of the present application, and it should be pointed out that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. The application of a carbon nitride-based copper single-atom photocatalyst in the phosphine hydrogenation reaction, characterized in that, Under illumination, using a carbon nitride-based copper single-atom photocatalyst as a catalyst, a phosphine hydroaddition reaction is catalyzed between phosphine hydrogen compounds and unsaturated hydrocarbons to obtain phosphorus-containing compounds. The carbon nitride-based copper single-atom photocatalyst is composed of a carbon nitride support and copper distributed in single-atom form, wherein the copper loading in the carbon nitride-based copper single-atom photocatalyst is 0.1 wt.% to 10 wt.%. Unsaturated hydrocarbons are unsaturated alkenes and / or unsaturated alkynes; The illumination conditions are one or more of the following: monochrome LED illumination, full-spectrum xenon lamp illumination, sunlight illumination, and laser illumination; The wavelength range of the illumination conditions is 254~800nm, and the light intensity of the illumination conditions is 1000~12000mW / cm². 2 ; The phosphine hydrogen compound has the structure shown in Formula IV: Formula IV; In the formula IV, R 1 and R 2 Selected independently from H, CH3, t One of the Bu; The unsaturated olefin has the structure shown in formula A1, A2, A3 or A4: Formula A1, Formula A2, Formula A3, Formula A4; In equations A1, A2, A3, and A4, n = 0~20, m = 0~20, o = 0~20, p = 0~20, and R in equations A1, A2, A3, and A4... 1 R 2 R 3 and R 4 Selected independently from H, CH3, t Bu、OMe、 , , , , , One of NH2, OH, F, Cl, Br and I; The unsaturated alkyne has the structure shown in formula B1 or B2, or is norethindrone; Formula B1, Formula B2; In equations B1 and B2, n = 0~20 and m = 0~20; In equations B1 and B2, R 1 and R 2 Selected independently from H, CH3, t Bu、OMe、 , , , , , One of NH2, OH, F, Cl, Br and I.

2. The application according to claim 1, characterized in that, The molar ratio of the phosphine hydrogen compound to the unsaturated hydrocarbon is (0.5~10):

1.

3. The application according to claim 1, characterized in that, The carbon nitride-based copper single-atom photocatalyst can be recycled and reused in batch reactions.

4. The application according to claim 1, characterized in that, The preparation method of the carbon nitride-based copper single-atom photocatalyst is one or more of the following: impregnation method, precipitation method, photoreduction method, hydrothermal synthesis method, and freeze-drying method.

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