CN115672373A - Bimetallic monoatomic carbon-based catalyst, preparation method and application thereof - Google Patents

Bimetallic monoatomic carbon-based catalyst, preparation method and application thereof Download PDF

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CN115672373A
CN115672373A CN202211334223.2A CN202211334223A CN115672373A CN 115672373 A CN115672373 A CN 115672373A CN 202211334223 A CN202211334223 A CN 202211334223A CN 115672373 A CN115672373 A CN 115672373A
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copper
palladium
catalyst
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陈玥光
董慧敏
汪乐余
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Beijing University of Chemical Technology
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Abstract

The invention discloses a bimetallic single-atom carbon-based catalyst, a preparation method and application thereof, wherein the carbon-based catalyst comprises a carbon-based carrier, the carrier loads two metal single atoms of palladium and copper, and the atomic ratio of the palladium to the copper is 0.1-1:0.1 to 1, and the average spacing between the palladium and copper atoms is 2.5 to 4.5 angstroms. The preparation method of the double-monatomic catalytic material is simple, pd and Cu double monatomics are used as reactive substances, and the nitrogen-doped carbon hollow nanospheres are used as carriers, so that the structure is stable, and the catalytic activity is high. The Sonogashira coupling reaction catalyzed by the catalytic material prepared by the invention has mild conditions, does not need to add a cocatalyst which is expensive and difficult to dissolve, shows good catalytic activity for chlorobenzene which is difficult to be activated, is a preparation method which accords with green chemistry and atom economy and has industrial synthesis value, obtains good technical effect, and provides a unique idea for the design of heterogeneous catalysts.

Description

Bimetallic monoatomic carbon-based catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of material preparation and catalysis, in particular to a bimetallic monatomic carbon-based catalyst, and a preparation method and application thereof.
Background
Csp can be realized by Sonogashira coupling reaction 2 The cross coupling with Csp is one of effective means for constructing carbon-carbon triple bonds, and plays an important role in the fields of organic total synthesis and industrial production. Traditional homogeneous catalysts rely on complex, toxic organophosphine ligands and the cost and recyclability of the catalyst has been an unsolved problem. The intrinsic activity of the existing heterogeneous catalyst is insufficient, an additional promoter which is difficult to dissolve and expensive is required to be added to improve the reaction selectivity, and the reaction usually requires higher temperature (such as 140 ℃) and longer reaction time (such as 10 hours); the consumption of noble metal is large, and the cost of the catalyst is high. In addition, the system often has side reactions and by-products such as self-coupling of substrate molecules, and has a problem of insufficient catalyst selectivity. It is also noteworthy that differences in the substituents of the substrates in the system often lead to differences in the ease of reaction. Compared with the coupling reaction of iodobenzene and phenylacetylene, the method has the advantages that the method is more difficult to realize the activation and participation of bromobenzene, especially chlorobenzene in the coupling reaction, most of the currently reported catalysts can only catalyze the coupling reaction of iodobenzene, and the method does not have good universality on the activation of different halogen substituted substrates. Therefore, it is important to find a catalyst for Sonogashira coupling reaction, which can ensure the reactivity and selectivity under mild reaction conditions.
As a monatomic catalyst for connecting bridges of homogeneous catalysis and heterogeneous catalysis, the catalyst has the characteristics of high activity, greenness, atom economy and easiness in recovery, and is a powerful competitor of an ideal catalyst. In addition, compared with a metal monoatomic catalyst, the bimetallic monoatomic catalyst has double-activity centers, the invention provides that two reactants can be respectively adsorbed on different atoms to react, and the spatial distribution and the electronic structure of two active sites can be regulated and controlled by regulating the proportion of metal precursor salt, so that the bimolecular reaction process in the Sonogashira coupling reaction can be effectively regulated, and the selectivity and the universality of the reaction can be obviously improved.
Disclosure of Invention
One of the problems to be solved by the invention is to solve the problems that the catalytic conditions in the prior Sonogashira coupling reaction are harsh and a cocatalyst is needed, and provide a novel catalyst and a synthetic method thereof. In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a bimetallic monatomic carbon-based catalyst, which comprises a carbon-doped nitrogen carrier, wherein the carrier loads two metal monatomics of palladium and copper, and the atomic ratio of the palladium to the copper is 0.1-1:0.1 to 1, the average spacing between palladium and copper atoms being 2.5 to 4.5 angstroms; preferably 2.5-3.5 angstroms. The invention creatively discovers that when the atomic ratio of Cu to Pd is close to 1:1, the number of the formed double monoatomic pairs is the most, and the average distance between the formed double monoatomic pairs meets the distance (namely 2.5-4.5 angstroms, preferably 2.5-3.5 angstroms) required by the coupling reaction, so that the cross coupling probability of the two reactants is increased, the self-coupling phenomenon of substrate molecules is effectively avoided, the selectivity of a target product is improved, and meanwhile, the method has good tolerance on substrate molecules with various different substituents, and can realize the diversity synthesis of various important compounds. The two active sites respectively adsorb and activate two reaction substrates, so that the reaction can be converted with high activity and high selectivity under the green conditions of low temperature, normal pressure, no promoter and the like, and the catalyst has higher catalytic activity on the reaction substrates of bromobenzene and chlorobenzene which are difficult to activate. Compared with the prior art, the method has the advantages of mild reaction conditions, convenience in operation, simple process, cheap and easily-obtained raw materials, wide applicability, reusability and the like, reduces the consumption of the noble metal by 1-3 orders of magnitude (compared with ACS appl. Meter. Interfaces 2015,7,3199-3206 series achievements and the like), has high utilization rate and high catalytic activity of the noble metal, and accords with the concepts of green chemistry and atomic economy. And the heterogeneous catalysis system does not need to add an organic homogeneous cocatalyst which is difficult to dissolve and expensive, thereby avoiding the problems of organic catalysts, auxiliary agents and the like and difficult separation and purification of products.
In a preferred embodiment of the present invention, the atomic ratio of palladium to copper is 0.5 to 1:0.5 to 1; preferably 0.7 to 1:0.7 to 1; more preferably 0.9 to 1:0.9-1. The invention creatively discovers that when the atomic ratio of two metals of copper and palladium is close to 1:1, the number of pairs of diatomic monoatomic pairs formed is the greatest and the average spacing between the two corresponds to the spacing required for the coupling reaction.
In a preferred embodiment of the present invention, the carbon-based carrier is a carbon and nitrogen material. The doping of nitrogen helps anchor the metal sites, which is not the case with common commercial carbon-based supports. According to the invention, by regulating the feed ratio of metal precursor salt and the strategy of doping N into the carbon material as a coordination anchoring site, the control of the spacing of active sites is facilitated, the obvious improvement of the selectivity of the Sonogashira coupling reaction is facilitated, a unique thought is provided for the design of a heterogeneous catalyst, and a new material and a new method are provided for organic synthesis reaction.
In a preferred embodiment of the present invention, the ratio of the weight of the carbon-based support to the sum of the weights of palladium and copper is 62500-45454. The invention can effectively reduce the cost of the catalyst on the basis of ensuring the catalytic activity by obviously reducing the content of the metal.
Another aspect of the present invention relates to a method for preparing the above carbon-based catalyst, comprising the steps of:
a. styrene, a surfactant and a thermal initiator are put in deionized water, heated, stirred and cooled, and the obtained precipitate is dispersed in a polar solvent after centrifugal washing;
b. b, taking the precipitate obtained in the step a as a template, adding a micromolecular carbon nitrogen compound and precursor salts of palladium and copper into a buffer solution with the pH value of 7-10, centrifuging, washing and drying to obtain a catalyst precursor;
c. calcining the product obtained in the step b at 700-900 ℃ to obtain a powdery sample; if the calcination temperature is too low, the PS sphere precursor is incompletely calcined, which can cause the residue of impurities, and if the calcination temperature is too high, the morphology of the carbon spheres can collapse, which can cause the embedding of the catalytic active sites
d. And c, carrying out acid treatment on the powdery sample obtained in the step c, centrifuging, washing and drying to obtain the double-monoatomic catalyst.
Preferably, the surfactant described in step a includes, but is not limited to, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), polyvinylpyrrolidone (PVP), sodium Dodecylbenzenesulfonate (SDBS), and the like.
Preferably, the thermal initiator used in step a includes, but is not limited to, inorganic peroxide initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like.
Preferably, the polar solvent used in step a includes, but is not limited to, methanol, ethanol, ethylene glycol, isopropanol, water, and the like.
Preferably, the metal copper salt in step b includes, but is not limited to, inorganic or organic metal copper salts, such as copper nitrate, copper acetate, copper chloride, copper sulfate, copper acetylacetonate, copper phthalocyanine, and the like.
Preferably, the metal palladium salt in step b includes, but is not limited to, inorganic or organic metal copper salt, palladium acetylacetonate, palladium sulfate, palladium chloride, and the like.
Preferably, the small molecule carbon nitrogen compound in step b includes, but is not limited to, melamine, dicyandiamide, pyridine, urea and cyanoguanidine.
Preferably, the drying temperature in step b is 30-100 ℃ and the drying time is 4-24h.
Preferably, the pH regulator in step b is one or more of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate.
Preferably, the calcination temperature time in step c is 0.5-10h, the heating rate is 2-10 ℃/min, and the calcination atmosphere is one of argon, helium, air and nitrogen.
Preferably, the acid in step d is diluted acid, including but not limited to hydrochloric acid, the temperature of acid treatment is 50-100 ℃ and the time is 2-48h, and the drying temperature is 30-100 ℃ and the time is 4-24h.
The invention also relates to the application of the catalyst in catalyzing the coupling reaction of phenylacetylene and halogenated benzene, which is characterized in that the dosage of the catalyst in the reaction is 1-3% of the mass of a reactant, the reaction temperature is 70-140 ℃, the reaction pressure is normal pressure but not limited to normal pressure, and the reaction time is 4-24h. Preferably, the reaction solvent is ethanol, which has higher reaction selectivity compared to other solvents (e.g., toluene, DMF). It should be noted that although the reaction pressure of the present invention is not limited to normal pressure, it is unexpected that the catalyst of the present invention can achieve high catalytic activity under normal pressure.
In a preferred embodiment of the present invention, the catalytic conversion rate of the reaction is 98% or more, and the selectivity of the reaction is 92% or more, preferably 94% or more.
In a preferred embodiment of the present invention, the halogenated benzene is selected from one or a combination of two or more of iodobenzene, chlorobenzene and bromobenzene.
The invention has the following beneficial results:
the supported catalyst with the structure of the adjacent coordination double monoatomic atoms is prepared by combining a template method, a wet impregnation method and a high-temperature calcination method, the difference of the number of double monoatomic pairs and the metal spacing in the catalyst is realized by regulating and controlling the feed ratio of two metal precursors, the active sites of the two metals are effectively regulated and controlled, and the selectivity of the catalyst for catalyzing Sonogashira coupling reaction is obviously improved. Compared with the prior art, the preparation method of the double-monatomic catalytic material is simple, stable in structure and high in catalytic activity, and the dosage of Pd is reduced by two orders of magnitude. The Sonogashira coupling reaction catalyzed by the catalytic material prepared by the invention has mild conditions, does not need to add a cocatalyst which is expensive and difficult to dissolve, and has good catalytic activity for chlorobenzene which is difficult to be activated, so the preparation method accords with green chemistry and atom economy and has industrial synthesis value, obtains good technical effect, and provides a unique thought for the design of heterogeneous catalysts.
Drawings
FIG. 1: reaction equation of Sonogashira coupling reaction.
FIG. 2 is a schematic diagram: pd prepared in example 1 54 Cu 46 Transmission electron micrographs of the/C-N diatomic monatomic catalyst.
FIG. 3: pd prepared in example 1 54 Cu 46 A spherical aberration correction high-resolution transmission electron microscope image of the/C-N double-monoatomic catalyst.
FIG. 4: pd prepared in example 1 54 Cu 46 The distance between two metal atoms of the/C-N double monoatomic catalyst.
FIG. 5: pd prepared in example 2 86 Cu 14 The distance between two metal atoms of the/C-N catalyst.
FIG. 6: pd prepared in example 3 37 Cu 63 The distance between two metal atoms of the/C-N double monoatomic catalyst.
FIG. 7: transmission electron micrographs of the Cu/C-N monatomic catalyst prepared in comparative example 1.
FIG. 8: transmission electron micrographs of the Pd/C-N monatomic catalyst prepared in comparative example 2.
FIG. 9: transmission electron microscopy images of PdCu alloy nanocatalysts prepared in comparative example 4.
FIG. 10: x-ray diffraction patterns of the Cu/C-N, pd/C-N monatomic catalysts prepared in comparative example 1 and comparative example 2.
FIG. 11: the X-ray diffraction pattern of the PdCu alloy nanocatalyst prepared in comparative example 3.
FIG. 12: a schematic of simultaneous fluorescence detection of the catalyzed reaction in example 4, wherein: (a) Pd 54 Cu 46 Synchronous fluorescence spectrum of the mixture after the/C-N catalytic reaction; (b) Synchronous fluorescence spectra of mixtures of phenylacetylene and tolane of different concentrations (black line: 0.2mmol/L, red line: 0.3mmol/L, blue line: 0.4mmol/L, green line: 0.5mmol/L and violet: 0.6 mmol/L); (c) standard curve of the reactant phenylacetylene; and (d) a standard curve of the target product tolane.
Detailed Description
Example 1
a. Dissolving 1.5g of PVP in deionized water, adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, and dispersing the PS ball precipitate in a polar solvent;
b. firstly, taking the precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the solution into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, respectively weighing 0.002mmol of sodium chloropalladate and 0.0105mmol of copper chloride, dissolving, adding the solution into the dispersion liquid 2, stirring for 24 hours at normal temperature, washing by using absolute ethyl alcohol, and drying;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere, and calcining for 2h to obtain a PdCu NPs/C-N material;
d. and C, putting the PdCu NPs/C-N material obtained in the step C into a sample bottle, adding a dilute nitric acid solution, and putting the sample bottle into a heating module for heat treatment at 80 ℃ for 24h to remove substances, such as metal oxides, metal nanoparticles and the like, of the two metals in other forms, so as to ensure that the two metals exist in a monoatomic form. After the reaction is finished, the Pd is obtained by centrifugal washing with absolute ethyl alcohol and deionized water 54 Cu 46 a/C-N bi-monatomic catalyst (Pd: cu = 54.
Example 2
a. Dissolving 1.5g of PVP in deionized water, adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, and dispersing the PS ball precipitate in a polar solvent;
b. firstly, taking the precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the solution into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, respectively weighing 0.0035mmol of sodium chloropalladate and 0.0035mmol of copper chloride, dissolving, adding the solution into the dispersion liquid 2, stirring for 24 hours at normal temperature, washing by using absolute ethyl alcohol, and drying;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere, and calcining for 2h to obtain a PdCu NPs/C-N material;
d. putting the PdCu NPs/C-N material obtained in the step C into a sample bottle, adding a dilute nitric acid solution, and putting the sample bottle into a heating module for heat treatment at 80 ℃ for 24 hours to remove substances, such as metal oxides, metal nanoparticles and the like, of the two metals in other forms, so as to ensure that the two metals exist in a form of single atomAt this point. After the reaction is finished, the Pd is obtained by centrifugal washing with absolute ethyl alcohol and deionized water 86 Cu 14 a/C-N double-monoatomic catalyst.
Example 3
a. Dissolving 1.5g of PVP in deionized water, adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, and dispersing the PS ball precipitate in a polar protic solvent;
b. firstly, taking the precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the solution into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, respectively weighing 0.0015mmol of sodium chloropalladate and 0.0015mmol of copper chloride, dissolving, adding the solution into the dispersion liquid 2, stirring for 24 hours at normal temperature, washing by using absolute ethyl alcohol, and drying;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere, and calcining for 2h to obtain a PdCu NPs/C-N material;
d. putting the PdCu NPs/C-N material obtained in the step C into a sample bottle, adding a dilute nitric acid solution, putting the sample bottle into a heating module, carrying out heat treatment at 80 ℃ for 24 hours to remove substances, such as metal oxides, metal nanoparticles and the like, of the two metals in other forms, ensuring that the two metals exist in a monoatomic form, and carrying out centrifugal washing by using absolute ethyl alcohol and deionized water to obtain Pd 37 Cu 63 a/C-N double-monoatomic catalyst.
Comparative example 1
a. Dissolving 1.5g of PVP in deionized water, adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, and dispersing the PS ball precipitate in a polar protic solvent;
b. firstly, taking the precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the solution into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, weighing 0.007mmoL of copper chloride, adding the copper chloride into the dispersion liquid 2 after dissolving, stirring the solution at normal temperature for 24 hours, washing the solution by using absolute ethyl alcohol, and drying the solution;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere, and calcining for 2 hours to obtain a Cu NPs/C-N monatomic catalyst;
d. and C, putting the Cu NPs/C-N material obtained in the step C into a sample bottle, adding a dilute nitric acid solution, putting the sample bottle into a heating module, carrying out heat treatment at 80 ℃ for 24 hours to remove substances, such as metal oxides, metal nanoparticles and the like, of the two metals in other forms, ensuring that the two metals exist in a monatomic form, and carrying out centrifugal washing by using absolute ethyl alcohol and deionized water after the completion to obtain the Cu/C-N monatomic catalyst.
Comparative example 2
a. Dissolving 1.5g of PVP in deionized water, then adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, dispersing the PS ball precipitate in the polar protic solvent;
b. firstly, taking the precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water after centrifugation to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the solution into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, weighing 0.007mmol of sodium chloropalladate, adding the solution into the dispersion liquid 2 after dissolution, stirring the solution at normal temperature for 24 hours, washing the solution by using absolute ethyl alcohol, and drying the solution;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere and calcining for 2h to obtain a Pd NPs/C-N material;
d. and d, putting the Pd NPs/C-N obtained in the step C into a sample bottle, adding a dilute nitric acid solution, putting the sample bottle into a heating module, carrying out heat treatment at 80 ℃ for 24 hours to remove substances, such as metal oxides, metal nanoparticles and the like, of the two metals in other forms, ensuring that the two metals exist in a monatomic form, and centrifugally washing the obtained product by using absolute ethyl alcohol and deionized water to obtain the Pd/C-N monatomic catalyst.
Comparative example 3
The materials synthesized in comparative example 1 and comparative example 2 were mixed in an amount of 1:1.
Comparative example 4
a. Dissolving 1.5g of PVP in deionized water, adding styrene and 110mg of ammonium persulfate, stirring for 4h at 70 ℃ in an oil bath, cooling, washing and centrifuging to obtain PS (polystyrene) ball precipitate, and dispersing the PS ball precipitate in a polar protic solvent;
b. taking a precipitation dispersion liquid obtained in the step a by using a liquid transfer gun, dispersing the precipitation dispersion liquid in a flask by using deionized water after centrifugation to obtain a dispersion liquid 1, dissolving 80mg of dopamine hydrochloride and 15mg of urea by using a buffer solution, adding the dopamine hydrochloride and 15mg of urea into the dispersion liquid 1 which is just obtained to obtain a dispersion liquid 2, respectively weighing 0.002mmol and 0.0105mmol of two metals, adding the two metals into the dispersion liquid 2 after dissolution, stirring the mixture for 24 hours at normal temperature, washing the mixture by using absolute ethyl alcohol, and drying the mixture;
c. transferring the dried precipitate into a porcelain boat, and placing the porcelain boat in N 2 Heating to 800 ℃ in the atmosphere, and calcining for 2h to obtain the PdCu alloy nano catalyst.
Example 4
20mg of Pd 54 Cu 46 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. The standard curves of the target product tolane and the reactant phenylacetylene are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 99%, and the selectivity of the target product tolane is 95.1%.
Example 5
20mg of Pd 86 Cu 14 Putting the/C-N double-monoatomic catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. The standard curves of the target product tolane and the reactant phenylacetylene are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 99%, and the selectivity of the target product tolane is 87.6%.
Example 6
20mg of Pd 37 Cu 63 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 49.8%, and the selectivity of the target product tolane is 99.1%.
Comparative example 5
Placing 20mg of Cu/C-N monatomic catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Respectively obtaining standard curves of target products of tolane and reactant of phenylacetylene by synchronous fluorescence detection, and detecting conversion rate<1.0%, no target product tolane was detected.
Comparative example 6
20mg of Pd/C-N monatomic catalyst and a stirrer are placed in a reaction tube, 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate are added, and N is introduced 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 99%, and the selectivity of the target product tolane is 82.9%.
Comparative example 7
Putting 10mg of Pd/C-N and 10mg of Cu/C-N two monatomic catalysts and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 As a protective gas and connecting a balloon sealing system at the mouth of the condenser at 100After the reaction is carried out for 5 hours by magnetic stirring, the reaction is stopped, and the catalyst and the supernatant are centrifugally separated after being cooled to room temperature. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 79.3%, and the selectivity of the target product tolane is 99.3%. The conversion of comparative example 7 is significantly lower compared to example 4 (atomic ratio of Pb and Cu close to that of comparative example 7).
Comparative example 8
Putting 10mg of PdCu alloy nano catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 100 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 0.78%, and the target product tolane is not detected.
Example 7
20mg of Pd 54 Cu 46 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of DMF, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for reaction for 5h, stopping the reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 21.5%, and the selectivity of the target product tolane is 85.8%.
Example 8
20mg of Pd 54 Cu 46 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of toluene, 0.5mmol of iodobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 80 ℃ for 5h, stopping reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Respectively obtaining target products of diphenyl-ethylene through synchronous fluorescence detectionThe standard curve of alkyne and reactant phenylacetylene shows that the detection conversion rate is 14.8 percent, and the selectivity of the target product tolane is 55.1 percent.
Example 9
20mg of Pd 54 Cu 46 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of DMF, 0.5mmol of bromobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 140 ℃ for reaction for 9h, stopping the reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 75.3%, and the selectivity of the target product tolane is 95.2%.
Example 10
20mg of Pd 54 Cu 46 Putting the/C-N double-monatomic catalyst and a stirrer into a reaction tube, adding 10mL of ethanol, 0.5mmol of chlorobenzene, 0.5mmol of phenylacetylene and 1mmol of anhydrous potassium carbonate, and introducing N 2 Connecting a balloon sealing system at the opening of a condensing tube as protective gas, magnetically stirring at 140 ℃ for reaction for 9h, stopping the reaction, cooling to room temperature, and centrifugally separating the catalyst and supernatant. Standard curves of a target product tolane and a reactant tolane are respectively obtained through synchronous fluorescence detection, the detection conversion rate is 39.6%, and the selectivity of the target product tolane is 94.9%.

Claims (10)

1. A bimetallic monatomic carbon-based catalyst comprising a carbon-based carrier supporting two metal monatomic atoms of palladium and copper in an atomic ratio of palladium to copper of 0.1-1 to 0.1-1, preferably in an atomic ratio of palladium to copper of 0.5-1:0.5 to 1; more preferably 0.7 to 1:0.7 to 1; particularly preferably 0.9 to 1:0.9 to 1; the average distance between palladium and copper atoms is 2.5-4.5 angstroms; preferably 2.5 to 3.5 angstroms.
2. The carbon-based catalyst according to claim 1, said carbon-based support being a carbon and nitrogen material.
3. The carbon-based catalyst according to claim 1, wherein the ratio of the carbon-based support to the total weight of palladium and copper is 62500-45454.
4. A process for the preparation of the carbon based catalyst according to any one of claims 1-3, comprising the steps of:
a. styrene, a surfactant and a thermal initiator are put in deionized water, heated, stirred and cooled, and the obtained precipitate is dispersed in a polar solvent after centrifugal washing;
b. b, taking the precipitate obtained in the step a as a template, adding micromolecular carbon nitrogen compound and precursor salt of palladium and copper into a buffer solution with the pH value of 7-10, and centrifugally washing and drying to obtain a catalyst precursor;
c. calcining the product obtained in the step b at 700-900 ℃ to obtain a powdery sample;
d. and c, carrying out acid treatment on the powdery sample obtained in the step c, and carrying out centrifugal washing and drying to obtain the double-monatomic catalyst.
5. The method of claim 4, wherein the surfactant in step a is selected from the group consisting of cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), polyvinylpyrrolidone (PVP), and Sodium Dodecylbenzenesulfonate (SDBS).
6. The method according to claim 4, wherein the thermal initiator in step a is an inorganic peroxide initiator.
7. The method of claim 4, wherein the small molecule carbon nitride compound in step b is selected from one or more of melamine, dicyandiamide, pyridine, urea and cyanoguanidine.
8. The use of the carbon-based catalyst according to any one of claims 1 to 3 for catalyzing the coupling reaction of phenylacetylene and halogenated benzene, wherein the amount of the catalyst used in the reaction is 1 to 3 percent of the mass of the reaction substance, and the reaction temperature is 70 to 140 ℃ and the reaction time is 4 to 24 hours.
9. The use according to claim 8, wherein the catalytic conversion of the reaction is above 98% and the selectivity of the reaction is above 92%.
10. The use according to claim 8 or 9, wherein the halogenated benzene is selected from one or a combination of more than two of iodobenzene, chlorobenzene and bromobenzene.
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