CN114713258B - Application of platinum monoatomic heterogeneous catalyst in hydrosilylation reaction - Google Patents

Application of platinum monoatomic heterogeneous catalyst in hydrosilylation reaction Download PDF

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CN114713258B
CN114713258B CN202210272788.6A CN202210272788A CN114713258B CN 114713258 B CN114713258 B CN 114713258B CN 202210272788 A CN202210272788 A CN 202210272788A CN 114713258 B CN114713258 B CN 114713258B
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platinum
heterogeneous catalyst
carbon nitride
hydrosilylation
catalyst
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CN114713258A (en
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宗绪鹏
孙再成
王金明
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Beijing University of Technology
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    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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Abstract

The invention provides an application of a platinum single-atom heterogeneous catalyst in hydrosilylation reaction, wherein the platinum single-atom heterogeneous catalyst consists of carrier carbon nitride or carbon nitride derivative and platinum loaded on the carrier carbon nitride or carbon nitride derivative and dispersed in a single-atom form, and the loading amount is 0.02-10 wt.%. The catalyst provided by the invention realizes the hydrosilylation reaction with high conversion rate and high selectivity under the condition of heating (less than 200 ℃) or visible light or heating and light. Especially, the hydrosilylation reaction driven by the irradiation of visible light has the characteristics of short induction period and high selectivity. The method has the advantages of mild reaction conditions, low energy consumption, high efficiency, good selectivity and high catalyst circulation stability, and the catalyst can be recycled after simple solid-liquid separation and can be used as a filler for realizing large-scale continuous flow mobile phase synthesis after solid-loading.

Description

Application of platinum monoatomic heterogeneous catalyst in hydrosilylation reaction
Technical Field
The invention relates to the field of organic chemical synthesis, in particular to application of a platinum single-atom heterogeneous catalyst in an optical drive hydrosilylation reaction.
Background
The hydrosilylation reaction refers to a reaction process in which H-Si is added on an unsaturated c=c double or triple bond of an aliphatic or aromatic organic compound, thereby constructing a carbon-silicon bond to synthesize an organosilicon compound, siloxane, or silicone resin. The reaction is the most important reaction in large-scale industrialized chemical synthesis, and the synthesized product has wide application in the fields of construction, textile, electronics, machinery, chemical industry, medical treatment and the like.
Currently, hydrosilylation catalysts in commercial production are mainly homogeneous catalysts with platinum salts or platinum complexes as active components, which are represented by Speier catalysts (H 2 PtCl 6 IPA) and Karstedt catalyst (Pt 2 [(Me 2 SiCH＝CH 2 ) 2 O] 3 ). However, these homogeneous catalysts are mostly not recovered after the reaction because they are uniformly dissolved in the reaction solvent and the reaction product, and the silicon chemistry industry consumes up to 5.6 tons of noble metal platinum per year because of the use of platinum-based homogeneous catalysts. On the one hand, the consumption of noble metal platinum is increasedLarge industrial costs and product prices (catalyst consumption about 30% of product price); on the other hand, in order to remove platinum remaining in the product, the cost of separation and purification is also greatly increased. From the aspect of catalytic performance, the homogeneous platinum catalyst is difficult to aggregate to generate platinum clusters and even platinum nano particles in the reaction process, and the platinum clusters and even platinum nano particles are dissolved in a catalytic system as colloid, so that side reactions are increased, the catalytic performance is reduced, the product is colored, and the product quality is reduced.
Heterogeneous catalysts have great advantages over homogeneous catalysts in recycling. In recent years, with the development of monoatomic catalysis, several heterogeneous catalysts for hydrosilylation have been developed. For example Pt/NR-Al 2 O 3 -IP(Cui,X.et al,ACS Cent.Sci.,2017,3,580.),Pt 1 /TiO 2 (Chen,Y.et al,J.Am.Chem.Soc.,2018,140,7407.),Pt 1 /N-doped-graphene(Zhu,Y.et al,ACS Catal.,2018,8,10004.),Pt 1 Humic acid derivatives (Liu, k.et al, angel.chem.int.ed., 2021,60,24220.), and the like. Heterogeneous single-atom catalysts can achieve performance comparable to or even superior to commercial homogeneous catalysts under certain specific substrates or reaction conditions, but in many cases are still inferior to commercial homogeneous catalysts. In the reaction mode, the heterogeneous single-atom catalyst and the homogeneous catalyst are heated to a certain temperature (50-200 ℃) to drive the reaction, so that the application of the heterogeneous single-atom catalyst under room temperature or low temperature conditions is limited.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an application of a platinum single-atom heterogeneous catalyst in hydrosilylation.
The invention provides an application of a platinum single-atom heterogeneous catalyst in hydrosilylation reaction, which consists of a carrier carbon nitride or carbon nitride derivative and platinum loaded on the carrier carbon nitride or carbon nitride derivative in a single-atom form distribution, wherein the platinum loading amount is 0.02-10 wt.%.
The platinum atoms in the catalyst and carbon and nitrogen atoms on the heptazine ring in the carbon nitride structure form weak coordination to form an activated catalytic active center. The two-dimensional lamellar structure of the carbon nitride has good space confinement effect, and can avoid the occurrence of platinum atom clustering. The surface of the carbon nitride is mainly a hydrophobic structure skeleton due to the characteristics of the organic polymer of the carbon nitride, and the carbon nitride has good compatibility with reactants and products of hydrosilylation, so that solvent-free reaction can be realized. The catalyst can drive the efficient and high-selectivity hydrosilylation under the heating condition, the illumination condition and the cooperation of heating and illumination.
The carbon nitride has a certain visible light response, and can drive hydrosilylation at room temperature or even low temperature under the irradiation of visible light. Since visible light does not excite the reactive molecules containing unsaturated carbon-carbon bonds, the selectivity of the product is not reduced by side reactions such as isomerization, hydrogenation or polymerization of unsaturated hydrocarbons. The reaction driven by visible light is rapid in initiation, high in activity and good in selectivity, and the terminal addition product can be efficiently and controllably generated.
The carbon nitride derivative is hetero-atom doped carbon nitride, defective carbon nitride, carbon nitride copolymer or heterojunction formed by carbon nitride and other materials.
The preparation method of the platinum single-atom heterogeneous catalyst comprises synthetic approaches including but not limited to an impregnation method, a precipitation method, a high-temperature decomposition method, a photo-reduction method, a hydrothermal synthesis method or a photo-induced ligand exchange method.
Wherein the light-induced ligand exchange method comprises the following synthesis steps:
s1, adding carbon nitride or a carbon nitride derivative and a platinum-complex precursor (PtLnXm), wherein the organic ligand L=triphenylphosphine (PPh) 3 ) Tritert-butylphosphine (P (t-Bu) 3 ) One or more of bipyridine (bpy), dibenzylideneacetone (dba), acetylacetone (acac), hexafluoroacetylacetone (hfac), trifluoroacetylacetone (tfac), dibenzoylacetone (dbm), benzoylacetone (bac), octa-1, 5-diene (cod), n=1-4; halogen X=Cl, br, m=0-3, adding into an organic solvent according to a mass ratio of 20:1-1000:1 (platinum-complex precursor is calculated by metal platinum mass), and forming a uniform dispersion by stirring or ultrasonic;
s2, removing the organic solvent at the temperature of 10-200 ℃ and/or under reduced pressure to obtain a platinum-complex precursor and carbon nitride or carbon nitride derivative mixed solid;
s3, dispersing the mixed solid into water, wherein the concentration range is 0.01-100mg/mL, and irradiating for 1-600 minutes by adopting illumination;
s4, filtering or centrifuging to obtain a solid subjected to light treatment, and drying at 50-200 ℃;
s5, cleaning the dried solid by using an organic solvent, removing unreacted platinum precursor and residual ligand, and drying again to obtain the platinum catalyst.
Further, in step S3, after dispersing the mixed solid into water, it is preferable to perform inert gas protection and then irradiation with light. Since oxygen may react with photogenerated electrons to be reduced when photoreduction is performed under air, an inert gas is used for protection against other interference.
The light-induced ligand exchange method can be used for synthesizing platinum on a carbon nitride or carbon nitride derivative carrier with high loading capacity.
The platinum single-atom heterogeneous catalyst is applied to hydrosilylation reaction, and specifically, the carbon nitride or the carbon nitride derivative loaded with platinum single atoms is used as a heterogeneous catalyst, and the hydrosilylation reaction is driven to occur between hydrogen-containing silane and unsaturated hydrocarbon under the condition of heating or illumination or under the photo-thermal synergistic condition.
In some embodiments of the invention, the hydrosilylation reaction is driven under heating conditions at a temperature in the range of 30-200 ℃.
In other embodiments of the present invention, the hydrosilylation reaction is driven under light conditions, the light being one or more of solar light irradiation, xenon light irradiation, LED light irradiation, and monochromatic laser light irradiation, the light wave wavelength being in the range of 300 to 800nm, preferably in the range of 400 to 550nm.
Further, the illumination intensity is 1-1000 mW/cm 2 . The temperature is controlled between minus 30 ℃ and 200 ℃ in the illumination process. When the hydrosilylation reaction of the invention adopts light driving, compared with thermal driving catalysis, the hydrosilylation reaction can be rapidly conducted under milder reaction conditionsReacting and crossing the energy barrier.
Further, the molar ratio of the hydrogen-containing silane to the unsaturated hydrocarbon is not less than 1:1.
Further, the molar ratio of the unsaturated hydrocarbon to the platinum in the platinum monoatomic heterogeneous catalyst is in the range of not less than 10:1-10 8 :1。
Further, the hydrogen-containing silane is:
wherein n=0-20, m=0-20, p=0-20, a=0-1000, b=0-1000, c=0-1000, r 1 ,R 2 ,R 3 Each independently selected from H, CH 3 ,NH 2 ,OH,Si(CH 3 ) 3 One of F, cl, br and I.
Further, the unsaturated hydrocarbon is alkene or alkyne, and when the unsaturated hydrocarbon is alkene, the structure is as follows:
R 1 ,R 2 ,R 3 ,R 4 each independently selected from H, CH 3 ,Ph,CH 3 O,C 2 H 5 O,O(SiOMe) 3 One of OH, F, cl, br, I; n, m, p, q=0-20.
When alkyne, its structure is:
R 1 ,R 2 each independently selected from H, CH 3 ,Ph,CH 3 O,C 2 H 5 O,O(SiOMe) 3 One of OH, F, cl, br, I; n, m, p=0-20.
The invention provides an application of a platinum single-atom heterogeneous catalyst in hydrosilylation. The platinum atom of the catalyst forms weak coordination with carbon and nitrogen atoms on a heptazine ring in a carbon nitride structure, and the platinum atom coordinated with the platinum atom is taken as a catalytic active center to have excellent activity and selectivity on hydrosilylation reaction. The two-dimensional lamellar structure of the carbon nitride can limit platinum atoms on the two-dimensional surface of the catalyst, so that the occurrence of platinum atom clustering is avoided, and the cycling stability of the catalyst serving as a heterogeneous catalyst is improved. The catalyst provided by the invention can be used under a heating condition, and can also drive a high-efficiency high-selectivity hydrosilylation reaction under an illumination condition or under the cooperation of heating and illumination. The hydrosilylation reaction driven by visible light irradiation has fast initiation and good selectivity. The catalyst has the advantages of mild reaction conditions, low energy consumption, high efficiency and good selectivity, and can be recycled after simple solid-liquid separation or used for large-scale flow synthesis after being immobilized as a filler.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The embodiment provides synthesis of a carbon nitride loaded platinum single-atom catalyst, and the preparation method comprises the following steps:
100mg of carbon nitride was added to 200mL of water and sonicated for 30min to form a uniform carbon nitride-water dispersion.
4.3mL of an aqueous solution of chloroplatinic acid (10 mg of chloroplatinic acid, 200mL of water) was added dropwise to the carbon nitride-water solution at a rate of 0.05mL/min by a syringe pump under stirring at room temperature.
After the completion of the dropwise addition, the temperature was raised to 70℃and the mixture was stirred for 5 hours with heating, followed by filtration and drying. The light yellow solid powder is obtained as the carbon nitride loaded platinum single-atom catalyst (numberPt 1 /CN-1). Platinum loading was 0.072wt.% as measured by ICP.
Example 2
The embodiment provides a synthesis method of a carbon nitride-titanium dioxide heterojunction supported platinum single-atom catalyst, which comprises the following steps:
1mL of an aqueous solution of platinum tetrammine nitrate (20 mg of platinum tetrammine nitrate, 200mL of water) was added to 100mg of the carbon nitride-titanium dioxide heterojunction solid with stirring at room temperature to form a viscous slurry and stirring overnight at room temperature until the water evaporated and was moved to a drying oven at 80℃for continued drying for 5 hours to dry the water completely.
Heating to 300 ℃ in a muffle furnace for 2 hours to obtain grey yellow solid powder, namely the carbon nitride-titanium dioxide heterojunction supported platinum monoatomic catalyst (number Pt 1 /CN-2). Platinum loading was 0.045wt.% by ICP.
Example 3
The embodiment provides a synthesis method of a defective carbon nitride supported platinum monoatomic catalyst, which comprises the following steps:
100mg of defective carbon nitride was added to 50mL of water, and sonicated for 30min to form a uniform carbon nitride-water suspension mixture.
25mL of an aqueous solution of chloroplatinic acid (50 mg of chloroplatinic acid, 50mL of water) was added dropwise to the carbon nitride-water solution at a rate of 0.05mL/min by a syringe pump under stirring at room temperature.
After completion of the dropwise addition, the mixed solution was cooled with liquid nitrogen, and after removing water by freeze-drying, it was heated to 300℃in a muffle furnace. The obtained grey yellow solid powder is the carbon nitride copolymer supported platinum single-atom catalyst (number Pt 1 /CN-3). Platinum loading was 9.8wt.% by ICP.
Example 4
The embodiment provides a synthesis method of a carbon nitride copolymer supported platinum monoatomic catalyst, which comprises the following steps:
100mg of carbon nitride copolymer was added to 50mL of water and sonicated for 30min to form a uniform carbon nitride-water suspension mixture.
10mL of an aqueous solution of platinum tetrammine nitrate (10 mg of platinum tetrammine nitrate, 10mL of water) was added dropwise to the carbon nitride-water solution by a syringe pump at a rate of 0.05mL/min with stirring at room temperature.
After the completion of the dropwise addition, the mixed solution was cooled with liquid nitrogen, and after the water was removed by freeze-drying, the solution was treated with a xenon lamp for 2 hours. Repeatedly cleaning the treated solid with water, centrifuging, and drying. The obtained grey yellow solid powder is the carbon nitride copolymer supported platinum single-atom catalyst (number Pt 1 /CN-4). Platinum loading was 4.4wt.% as measured by ICP.
Example 5
The embodiment provides synthesis of a carbon nitride loaded platinum single-atom catalyst, and the preparation method comprises the following steps:
100mg of carbon nitride copolymer was added to 50mL of water and sonicated for 30min to form a uniform carbon nitride-water suspension mixture.
10mL of an aqueous solution of chloroplatinic acid (20 mg of chloroplatinic acid, 10mL of water) was added dropwise to the carbon nitride-water solution at a rate of 0.1mL/min by a syringe pump under stirring at room temperature.
After the completion of the dropwise addition, the mixed solution was cooled with liquid nitrogen, and after the water was removed by freeze-drying, the solution was treated with a xenon lamp for 2 hours. Repeatedly cleaning the treated solid with water, centrifuging, and drying. The light yellow solid powder is obtained as the carbon nitride loaded platinum single-atom catalyst (number Pt 1 /CN-5). Platinum loading was 4.1wt.% by ICP.
Example 6
The embodiment provides a synthesis method of a carbon nitride copolymer supported platinum monoatomic catalyst, which comprises the following steps:
100mg of the carbon nitride copolymer was dispersed in 20mL of chloroform, and then 15mg of platinum acetylacetonate was added thereto, followed by mixing and stirring for 3 hours. Chloroform was removed by rotary evaporation and dried in an oven at 100deg.C for 5 hours.
The resulting dry solid was dispersed in 100mL of water, replaced with argon, and illuminated under a xenon lamp for 8 hours. The light-treated solid was centrifuged and dried in an oven at 100℃for 5 hours.
Repeatedly cleaning the solid powder with chloroform after the temperature is reduced to room temperature, and drying in an oven at 100deg.C for 5 hr to obtain orange solid powder which is nitridingCarbon copolymer supported platinum monoatomic catalyst (number Pt 1 /CN-6). Platinum loading was 5.7wt.% by ICP.
Application example 1
The heterogeneous catalyst Pt obtained in example 1 1 CN-1 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-1 was added to a 20mL reaction flask containing triethoxysilane and octene, heated to 90℃and reacted for 10 hours, cooled and filtered to separate the catalyst solid, and a colorless transparent product was obtained. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 2
The heterogeneous catalyst Pt obtained in example 2 1 CN-2 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-2 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 5 hours of visible light illumination by a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 3
The heterogeneous catalyst Pt obtained in example 3 1 CN-3 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-3 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 10 minutes of illumination with 430nm LED, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 4
The heterogeneous catalyst Pt obtained in example 4 1 CN-4 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-4 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 20 minutes of visible light illumination by a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 5
The heterogeneous catalyst Pt obtained in example 5 1 CN-5 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-5 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 10 minutes of visible light illumination at 60℃and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 6
The heterogeneous catalyst Pt obtained in example 6 1 CN-6 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-6 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 5 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 7
The heterogeneous catalyst Pt used in application example 6 1 The CN-6 is used for recycling in the hydrosilylation batch reaction, and specifically comprises the following steps:
10mg of used Pt was used 1 CN-6 was added to a 20mL reaction flask containing triethoxysilane and octene, and after 5 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%. The separated catalyst is subjected to the above-mentioned catalytic process for 10 times, and the catalytic activity is unchanged.
The structural formula of the product is as follows:
application example 8
The heterogeneous catalyst Pt obtained in example 6 1 CN-6 is used in continuous flow hydrosilylation reactions, and is specifically as follows:
20mgPt 1 CN-6 and 1g of silica microspheres were packed in a 20cm radius 1mm transparent quartz reaction tube, and a mixed liquid of triethoxysilane and octene mixed in a mass ratio of 1:1 was passed through the reaction tube at a rate of 0.5mL/min while a xenon lamp was visible light-irradiated to the reaction tube. The colorless transparent liquid led out after passing through the illumination reaction tube is the product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%. The continuous flow reaction was run for 10 hours with no change in catalytic activity.
The structural formula of the product is as follows:
application example 9
The heterogeneous catalyst Pt obtained in example 5 1 CN-5 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-5 was added to a 20mL reaction flask containing triethoxysilane and allylbenzene, and the flask was allowed to stand at room temperature under a xenon lampAfter 25 minutes of light exposure, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 10
The heterogeneous catalyst Pt obtained in example 3 1 CN-3 is used in continuous flow hydrosilylation reactions, and is specifically as follows:
20mgPt 1 CN-3 and 1g of silica microspheres were packed in a 20cm radius 1mm transparent quartz reaction tube, and a mixed liquid of dimethylphenylhydrosilane and octene, which were mixed in a mass ratio of 1:1, was passed through the reaction tube at a rate of 0.2mL/min while a xenon lamp was visible light-irradiated to the reaction tube. The colorless transparent liquid led out after passing through the illumination reaction tube is the product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%. The continuous flow reaction was run for 10 hours with no change in catalytic activity.
The structural formula of the product is as follows:
application example 11
The heterogeneous catalyst Pt obtained in example 4 1 CN-4 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-4 was added to a 20mL reaction flask containing tris (trimethylsiloxy) hydrosilane and octene, and after 3 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 12
The heterogeneous catalyst Pt obtained in example 6 1 CN-6 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-6 was added to a 20mL reaction flask containing cyclohexene oxide and dimethylphenylhydrosilane, and after 15 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 13
The heterogeneous catalyst Pt obtained in example 1 1 CN-1 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-1 was added to a 20mL reaction flask containing trichlorosilane and octene, and after 12 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to obtain a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 14
The heterogeneous catalyst Pt obtained in example 4 1 CN-4 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-4 was added to a 20mL reaction flask containing trimethoxysilane and octene, and after 10 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 15
The heterogeneous catalyst obtained in example 5Catalyst Pt 1 CN-5 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-5 was added to a 20mL reaction flask containing triethoxysilane and octadecene, and after 12 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to obtain a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 16
The heterogeneous catalyst Pt obtained in example 6 1 CN-6 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-6 was added to a 20mL reaction flask containing triethoxysilane and hexenes, and after 3 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 17
The heterogeneous catalyst Pt obtained in example 4 1 CN-4 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-4 was added to a 20mL reaction flask containing triethoxysilane and allyl methacrylate, and after 10 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 18
Will be described in detail below2 heterogeneous catalyst Pt 1 CN-2 is used in hydrosilylation batch reactions, and is specifically as follows:
10mgPt of 1 CN-2 was added to a 20mL reaction flask containing triethoxysilane and isoprene, and after 15 minutes of visible light irradiation at room temperature and a xenon lamp, the catalyst solid was separated by filtration to obtain a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 19
The heterogeneous catalyst Pt obtained in example 3 1 CN-3 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-3 was added to a 20mL reaction flask containing methyldiethoxyhydrosilane and octene, and after 10 minutes of visible light illumination at room temperature and in a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
application example 20
The heterogeneous catalyst Pt obtained in example 4 1 CN-4 was used in the hydrosilylation batch reaction, as follows:
10mgPt of 1 CN-4 was added to a 20mL reaction flask containing triisopropylhydrosilane and octene, and after 20 minutes of visible light illumination at room temperature and a xenon lamp, the catalyst solid was isolated by filtration to give a colorless transparent product. The GC-MS detection shows that the hydrosilylation yield is 99% and the terminal addition product selectivity is 99%.
The structural formula of the product is as follows:
finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The application of a platinum single-atom heterogeneous catalyst in hydrosilylation reaction is characterized in that the platinum single-atom heterogeneous catalyst consists of carrier carbon nitride or carbon nitride derivative and platinum loaded on the carrier carbon nitride or carbon nitride derivative in a single-atom form distribution, wherein the platinum loading amount is 0.02-10 wt%; the platinum single-atom heterogeneous catalyst drives the hydrosilane and the unsaturated hydrocarbon to generate hydrosilylation under the synergistic condition of illumination or heating and illumination.
2. The use of a platinum single-atom heterogeneous catalyst according to claim 1, wherein the carbon nitride derivative is a hetero-atom doped carbon nitride, a defective carbon nitride, a carbon nitride copolymer or a heterojunction formed by carbon nitride and other materials.
3. The use of a platinum monoatomic heterogeneous catalyst according to claim 1 in a hydrosilylation reaction, wherein the hydrosilylation reaction is driven under illumination, the illumination being one or more of solar light irradiation, xenon lamp illumination, LED illumination and monochromatic laser illumination, and the wavelength of light being in the range of 300-800 nm.
4. Use of a platinum monoatomic heterogeneous catalyst according to claim 3, characterised in that the wavelength of light is in the range 400-550nm in hydrosilylation reactions.
5. Use of a platinum monoatomic heterogeneous catalyst according to claim 3 in hydrosilylation reactions, characterised in thatWherein the illumination intensity is 1-1000 mW/cm 2 。
6. The use of a platinum monoatomic heterogeneous catalyst according to claim 5, characterized in that the temperature is controlled between-30 and 200 ℃ during the illumination process.
7. The use of a platinum monoatomic heterogeneous catalyst according to claim 1, characterised in that the molar ratio between the hydrogen-containing silane and the unsaturated hydrocarbon is not lower than 1:1;
the molar ratio of the unsaturated hydrocarbon to the platinum in the platinum monoatomic heterogeneous catalyst ranges from 10:1 to 10 10 :1。
8. The use of a platinum monoatomic heterogeneous catalyst according to claim 1, characterised in that the hydrogen-containing silane is:
wherein n=0-20, m=0-20, p=0-20, a=0-1000, b=0-1000, c=0-1000, r 1 ,R 2 ,R 3 Each independently selected from H, CH 3 ,NH 2 ,OH,Si(CH 3 ) 3 One of F, cl, br and I.
9. The use of a platinum monoatomic heterogeneous catalyst according to claim 1, characterized in that the unsaturated hydrocarbon is an olefin having the structure:
R 1 ,R 2 ,R 3 ,R 4 each independently selected from H, CH 3 ,Ph,CH 3 O,C 2 H 5 O,O(SiOMe) 3 One of OH, F, cl, br, I; n, m, p, q=0-20;
alternatively, the unsaturated hydrocarbon is alkyne, and the structure is:
R 1 ,R 2 each independently selected from H, CH 3 ,Ph,CH 3 O,C 2 H 5 O,O(SiOMe) 3 One of OH, F, cl, br, I; n, m, p=0-20.
10. The use of a platinum monoatomic heterogeneous catalyst according to claim 1 in hydrosilylation reactions, characterized in that the platinum monoatomic heterogeneous catalyst is recycled in batch reactions or as a reaction fixed bed in continuous flow synthesis.
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CN1500550A (en) * 2002-11-12 2004-06-02 中国科学院固体物理研究所 Solid-carrying type silicon hydrogen catalyst for additive reaction and preparation thereof
CN108699336A (en) * 2015-12-03 2018-10-23 艾伦塔斯贝克有限公司 One pack system, stable storing can UV cross-linked silicone silicone compositions
CN108722463A (en) * 2018-05-08 2018-11-02 陕西科技大学 A kind of pt atom modification nano-sheet carbon nitride photocatalyst and preparation method thereof
CN109796599A (en) * 2019-01-28 2019-05-24 广东工业大学 A kind of elastomer silicone and preparation method thereof using the synthesis of ultraviolet catalytic hydrosilylation
CN110452259A (en) * 2019-07-24 2019-11-15 杭州师范大学 A kind of method of light-initiated hydrosilylation

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CN1500550A (en) * 2002-11-12 2004-06-02 中国科学院固体物理研究所 Solid-carrying type silicon hydrogen catalyst for additive reaction and preparation thereof
CN108699336A (en) * 2015-12-03 2018-10-23 艾伦塔斯贝克有限公司 One pack system, stable storing can UV cross-linked silicone silicone compositions
CN108722463A (en) * 2018-05-08 2018-11-02 陕西科技大学 A kind of pt atom modification nano-sheet carbon nitride photocatalyst and preparation method thereof
CN109796599A (en) * 2019-01-28 2019-05-24 广东工业大学 A kind of elastomer silicone and preparation method thereof using the synthesis of ultraviolet catalytic hydrosilylation
CN110452259A (en) * 2019-07-24 2019-11-15 杭州师范大学 A kind of method of light-initiated hydrosilylation

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