CN111774096B - Catalyst modified by thiol ligand and preparation method and application thereof - Google Patents
Catalyst modified by thiol ligand and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst modified by thiol ligands and a preparation method and application thereof4S or Pd4S/X, preparation to obtain M-Pd4S catalyst or M-Pd with carrier4S/X catalyst, the catalyst prepared by the invention realizes intermediate alkynylation in alkyne semi-hydrogenation reactionThe compound has high selectivity, and meanwhile, the preparation method of the catalyst is simple to operate and has universality.
Description
The technical field is as follows: the invention relates to a catalyst, in particular to a catalyst modified by a thiol ligand, a preparation method and application thereof.
Background
The selective hydrogenation of alkynes plays an important role in catalysis in the aspects of fine chemical synthesis, drug synthesis, health product development and agrochemical synthesis, and the development of sustainable catalysts draws great attention in order to obtain high-yield target products and ensure that the reaction process is economical, practical, energy-saving and environment-friendly.
Conventionally, in industrial applications, in order to improve the selectivity of the product, the highly active metal is generally selectively protected by organic or inorganic substances, and this strategy is called "metal poisoning". In general, there are two strategies for selective hydrogenation poisoning: (1) synthesizing a multi-metal nano material to generate an electronic effect so as to influence the adsorption of reactants or products; for example, for the gas phase acetylene hydrogenation reaction, the industrial catalyst is generally Pd-Ag, Pd-Au, Pd-Bi, Pd-Cu, Pd-Ga, PdSn, Pd-Zn, etc., for the hydrogenation of nitro compounds, Pb, V or other compounds containing P, N, S or Cl, as well as Pt-Cr, Pt-Mn, Pt-Fe, Pt-Co, Pt-Ni, Pt-Au, Pt-Pd, Pt-Zn, Pt-Pb, Pt-V, etc., are generally modified on Pt; (2) the metal nanoparticles are surface modified to produce metal-ligand interactions that then affect the selectivity of the catalyst. For example, for the liquid phase hydrogenation of alkynes, Pd/CaCO, the surface of which is poisoned by Pb and quinoline, is generally used3I.e., Lindlar catalyst. A Pd-Pb nanocrystalline catalyst is prepared by a seed method through the poisoning effect of Pb on the surface of Pd, so that the catalyst has the effect of P-phenylacetylene on p-phenylacetyleneGood selectivity, but the poisoning effect of Pb makes the hydrogenation activity of the Pd-Pb catalyst poor. Patent CN101428228A discloses a selective hydrogenation catalyst, in which the active component of the catalyst is palladium, assistant copper, and alumina is used as carrier, the catalyst is suitable for removing alkyne by selective hydrogenation rich in alkyne residue, and the carrier treatment and preparation thereof require high temperature above 900 ℃. Patents CN1176291 and CN102688783A use honeycomb material and alumina silicon carbide as carriers, both use palladium as active main component and alkali metal and alkaline earth metal as auxiliary agent to realize high selectivity of semi-hydrogenation of alkyne, but these are both directed to selective semi-hydrogenation of terminal alkyne, which occurs in petroleum cracking in petrochemical field, and are not selective semi-hydrogenation of intermediate alkyne.
For heterogeneous catalysts, selectivity is generally due to electronic effects from changes in the metal's surrounding environment and steric effects from surface modifications. Because of the high activity of palladium, the traditional method usually needs to poison partial sites to have good selectivity to alkyne, which leads to the low activity of the catalyst and increases the use of noble metals, thereby increasing the cost; on the other hand, the preparation method of the selective hydrogenation catalyst is complicated, and particularly, the method of only carrying out the semi-hydrogenation reaction on the intermediate alkyne is difficult to be applied and produced on an industrial scale. Therefore, the excellent catalyst with the intermediate alkyne selective semi-hydrogenation activity can be prepared, the activity of the reaction can be improved by fully utilizing the active center of the catalyst, the operation is simple and convenient, the preparation cost of the catalyst is reduced, and the catalyst has important significance and value for industrial application.
Disclosure of Invention
An object of the present invention is to solve the existing problems and to provide a catalyst.
Another object of the present invention is to provide a method for preparing a catalyst.
It is also an object of the present invention to provide a catalyst application.
The invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst modified with a thiol ligandThe general formula of the catalyst is M-Pd4S or M-Pd4S/X; m is a thiol ligand and is used for modifying Pd4S; and the X is a carrier.
Preferably, the vector X is selected from C, CaCO3、α-Al2O3、γ-Al2O3At least one of cerium oxide, molecular sieves, silicon oxide, titanium oxide and diatomaceous earth.
Preferably, the thiol ligand M is at least one selected from the group consisting of linear thiols and aromatic thiols.
Further preferably, the linear thiol is at least one selected from the group consisting of n-butylthiol, thioglycolic acid, n-hexylthiol, 1-octylthiol, and dodecylthiol; the aromatic thiophenol is at least one selected from thiophenol, 3, 4-difluorothiophenol, 1-chlorothiophenol, 3, 4-dimethylthiophenol and 4-tert-butylthiophenol.
In a second aspect, the present invention provides a method for preparing a catalyst modified with a thiol ligand, comprising: the method comprises the following steps:
pd is added4S or Pd4Dispersing S/X in polar organic solvent, introducing hydrogen-containing gas and maintaining gas atmosphere, adding thiol ligand M, stirring, vacuum filtering, and drying to obtain M-Pd4S catalyst or M-Pd4And (3) an S/X catalyst.
Preferably, the polar organic solvent is selected from at least one of DMF, acetonitrile and alcoholic solvents.
Preferably, the hydrogen-containing gas atmosphere consists of hydrogen and protective gas in a volume ratio of 1: 0-4, the pressure of the gas atmosphere is 0.5-5 atm, further preferably, the hydrogen and the protective gas in a volume ratio of 1: 0-1, and the protective gas is selected from Ar and N2One kind of (1).
Preferably, the molar ratio of the thiol ligand M to Pd is (0.02-1.1) to 1.
More preferably, the molar ratio of the thiol ligand M to Pd is (0.1-0.8) to 1.
Preferably, the stirring time is 10min-12 h.
Preferably, the temperature of the stirring is 50 to 120 ℃.
Further preferably, the temperature of the stirring is 60 to 100 ℃.
The third aspect of the invention also provides an application of the catalyst or the catalyst obtained by the preparation method, which is applied to semi-hydrogenation of intermediate alkyne compounds.
Preferably, the intermediate alkyne compound is at least one selected from the group consisting of 1-phenyl-1-propyne, 1-phenyl-1-pentyne, tolane, 4-phenyl-3-butyn-2-one, 4-octyne, 3-phenyl-2-propyne-1-ol, and methyl phenylpropargyrate.
Preferably, the molar ratio of the intermediate alkyne compound to Pd is (1000-4000) to 1.
A method for applying a catalyst to semi-hydrogenation of an intermediate alkyne compound comprises the following steps:
transferring the polar organic solvent into a reaction bottle, selecting an intermediate alkyne compound as a substrate, placing the substrate into the reaction bottle for dispersion, setting the temperature to be 20-80 ℃, adding the catalyst, replacing hydrogen, keeping the hydrogen pressure of 1-3 atmospheres and stirring, wherein the molar ratio of the substrate to Pd is (1000-4000) to 1.
The alkyne hydrogenation is generally divided into two steps of hydrogenation, wherein the first step of alkyne hydrogenation is to generate alkene, and then further the alkene is deeply hydrogenated to generate alkane.
Chemical modification refers to the attachment of active groups or catalytic substances to the surface of an object to be modified by adsorption, coating, polymerization, chemical reaction, or other methods.
Preparation of the catalyst of the invention Pd4S can be selected from nano-scale materials, and the shapes of the S include but are not limited to particles, sheets and rods.
The invention adopts Pd4S or Pd4And modifying a ligand with large steric hindrance by the S/X to realize adsorption of alkyne and desorption of olefin so as to achieve high selectivity of olefin. Introducing gas containing hydrogen and keeping the gas atmosphere, and modifying Pd by using thiol ligand M4S or Pd4S/X, preparation to obtain M-Pd4S catalyst or M-Pd with carrier4The S/X catalyst is utilized to realize high selectivity to intermediate alkyne compounds in alkyne semi-hydrogenation reaction.
Has the advantages that:
(1) pd under hydrogen-containing gas atmosphere4S or Pd4After the thiol ligand is modified by S/X, the prepared catalyst has high selectivity on semi-hydrogenation of the intermediate alkyne compound, and the selectivity can reach more than 97%.
(2) The catalyst has high conversion rate of the semi-hydrogenation reaction of the intermediate alkyne compound, and the conversion rate can reach more than 99 percent.
(3) The catalyst prepared by the method has high stability, is not obviously inactivated after being applied for multiple times, and can still reach more than 98% in selectivity after being applied for 8 times.
(4) The modified thiol ligand used for preparing the catalyst has the advantages of small amount, low price, good reproducibility and stability, cost reduction and contribution to industrial application.
(5) The preparation method of the catalyst is simple to operate, simple and convenient in process and universal.
Drawings
FIG. 1(a) is a graph showing the conversion and selectivity of the semi-hydrogenation reaction of Pd Ns in example 1 using 1-phenyl-1-propyne as a substrate;
FIG. 1(b) shows Pd in example 14A conversion rate and selectivity curve diagram of the semi-hydrogenation reaction of the S Ns by taking 1-phenyl-1-propyne as a substrate;
FIG. 1(c) shows M-Pd in example 14Transformation rate and selectivity curve chart of semi-hydrogenation reaction of S Ns catalyst by using 1-phenyl-1-propyne as substrate (M is n-butyl mercaptan).
FIG. 2 shows the IR spectrum before and after modification of n-butylmercaptan in example 2, and (1) shows the peak of n-butyl group appearing after modification of n-butylmercaptan.
FIG. 3 is a chromatogram for the detection of products by gas chromatography with timed sampling in example 2.
FIG. 4 shows M-Pd in example 34S/γ-Al2O3Experimental sleeve for semi-hydrogenation reaction of catalystResults of 8 cycles of stability experiments (M is n-butylmercaptan).
FIG. 5 shows Pd/γ -Al in comparative example 12O3Conversion and selectivity profiles for the semi-hydrogenation experiments.
FIG. 6 shows Pd in comparative example 14S/γ-Al2O3Conversion and selectivity profiles for the semi-hydrogenation experiments.
FIG. 7 shows M-Pd in comparative example 14S/γ-Al2O3Conversion and selectivity profiles of the catalyst for the semi-hydrogenation experiments (M is n-butylmercaptan).
Figure 8 is an XRD pattern of the catalyst obtained in the first set of experiments in comparative example 2.
Figure 9 is an XRD pattern of the catalyst obtained in the second set of experiments in comparative example 2.
FIG. 10 is a transmission electron micrograph of the catalysts prepared in the first set of experiments of comparative example 2, as characterized by transmission electron microscopy.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solutions of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1: semi-hydrogenation reaction of catalyst prepared from two-dimensional palladium nanosheet
S1: pd is added4Dispersing the S Ns in a DMF solvent, introducing hydrogen with 1 hydrogen atmosphere for reaction for 10min, keeping the gas atmosphere, adding n-butylmercaptan as a thiol ligand M to ensure that the molar ratio of M to Pd is 0.4: 1, stirring for 60min at 80 ℃, leaching out the catalyst, washing and drying with ultrapure water for 12h to prepare the M-Pd4The S Ns catalyst was kept ready (M is n-butylmercaptan).
S2: PdNs and Pd with the same Pd molar mass4S Ns and M-Pd prepared from S Ns4The S Ns catalyst respectively takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, ultrasonically dispersing for 1min, setting the temperature at 30 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
FIG. 1 shows (a) Pd Ns and (b) Pd4S Ns and (c) M-Pd4S Ns catalyst are used for carrying out a conversion rate and selectivity curve of a semi-hydrogenation reaction on 1-phenyl-1-propyne.
Example 2
S1: pd is added4S/γ-Al2O3Dispersing in DMF solvent, introducing 1 hydrogen gas at atmospheric pressure for reaction for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make molar ratio of M to Pd 0.4: 1, stirring for 60min at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12 hr, and making into M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan). FIG. 2 is an infrared spectrum before and after modification of n-butylthiol, and it can be seen that a peak of n-butyl appears around 1400cm-1 after modification of n-butylthiol, indicating that n-butylthiol modification is successful.
S2: the prepared M-Pd4S/γ-Al2O3The catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. The timing sampling is carried out to detect the product by gas chromatography, and figure 3 is a chromatogram for the timing sampling to detect the product by gas chromatography, which shows that the product of the catalyst of the invention used in the semi-hydrogenation reaction is olefin.
Example 3: stability of the catalyst application of the invention
S1: pd is added4S/γ-Al2O3Dispersing in DMF solvent, introducing hydrogen gas with 1 atm of hydrogen gas to react for 10min,keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make M to Pd molar ratio 0.4: 1, stirring for 60min at 90 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12h to obtain M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
S3: the prepared catalyst is continuously recycled for 8 times. FIG. 4 shows M-Pd4S/γ-Al2O3The result of the 8 times circulation stability experiment applied to the catalyst in the semi-hydrogenation reaction experiment is shown in the figure, and the conversion rate and selectivity curve is shown in the figure 4, so that the selectivity of the catalyst is still more than 98% after the catalyst is applied for 8 times, and the stability is good.
Example 4
S1: pd is added4Dispersing S/X in a DMF solvent, introducing hydrogen with one atmospheric pressure of hydrogen to react for 10min, keeping the gas atmosphere, adding n-butyl mercaptan as a mercaptan ligand M, and enabling the ratio of M: the mole ratio of Pd is 0.4: 1, the stirring time is 60min, the stirring temperature is 80 ℃, the catalyst is filtered out by suction, and the M-Pd is prepared after washing and drying for 12h by ultrapure water4The S/X catalyst was kept ready (M is n-butylmercaptan).
S2: Pd/X with the same Pd molar mass and the prepared M-Pd4The S/X catalyst respectively takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, placing 2mmol of substrate into the reaction bottle, ultrasonically dispersing for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing hydrogen for 3 times, keeping 1bar of hydrogen in the reaction bottle, and setting the rotating speed at 1000rpm and turn on the stirrer. Table 1 is a data table of experimental results of semi-hydrogenation reactions performed on catalysts prepared by different carriers, and it can be seen that the catalysts prepared by different carriers according to the preparation method of the present invention have selectivity of more than 98% in semi-hydrogenation reactions, and have high selectivity.
TABLE 1 data of experimental results of semi-hydrogenation reactions on catalysts prepared with different carriers
In this embodiment, the carrier may also be molecular sieve, silica, titania, and diatomaceous earth.
Example 5
S1: pd is added4S/γ-Al2O3Dispersing in DMF solvent, introducing hydrogen gas with one hydrogen atmosphere pressure for reaction for 10min, keeping the gas atmosphere, adding different thiol ligands M to make the molar ratio of M to Pd (0.02-1.1) to 1, stirring for 10min-12h at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12h to obtain M-Pd4S/γ-Al2O3The catalyst is ready for use. The different experimental preparation conditions are shown in table 2 below.
S2: the prepared M-Pd4S/γ-Al2O3The catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
Preparation of M-Pd by using different types of thiol ligands, different using amounts of thiol ligands and different stirring times4S/γ-Al2O3The experimental results of the catalyst used in the semi-hydrogenation reaction are shown in table 2 below. It can be seen that: different thiol ligands can modify Pd4S, different thiol ligands have different steric hindrance effects onDifferent substrates may work differently, but all can significantly improve the selectivity for semi-hydrogenation of the intermediate acetylenic compound. The amount of thiol ligand used for modification also has an effect, and when the molar ratio of thiol ligand M to Pd is (0.02-1.1) to 1, alkyne conversion occurs>The selectivity of olefin is high at 99%, and the selectivity reaches more than 98%, wherein the optimum range of the dosage of the mercaptan ligand is (0.1-0.8) to 1. In addition, the stirring time is influenced to a certain extent, wherein when the stirring time is 10min-12h, the alkyne is converted>The selectivity of olefin reaches more than 98% when the selectivity is 99%, which is the best range.
TABLE 2 preparation of M-Pd with different kinds of thiol ligands, different amounts of thiol ligands and different stirring times4S/γ-Al2O3Experimental results data for semi-hydrogenation reactions
Example 6
S1: pd is added4S/γ-Al2O3Dispersing the catalyst in DMF solvent, introducing hydrogen gas with hydrogen atmospheric pressure for reaction for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make the molar ratio of M to Pd 0.4: 1, stirring for 12h at 50-120 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12h, and making into M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction flask, placing 2mmol of substrate into the reaction flask, ultrasonically dispersing for 1min at 60 deg.C, adding corresponding amount of catalyst at substrate-pd molar ratio of 2000: 1, and replacing for 3 timesAfter the hydrogen, 1bar of hydrogen was kept in the reaction flask, the rotation speed was set at 1000rpm and the stirring was switched on.
Table 3 shows the preparation of M-Pd at different stirring temperatures4S/γ-Al2O3The experimental result data of the catalyst used for the semi-hydrogenation reaction can show that the alkyne is converted when the stirring temperature is 50-120 DEG C>The selectivity of olefin reaches more than 98% when the content is 99%, and alkyne conversion is carried out when the stirring temperature is less than 60 ℃ and when the stirring temperature is more than 100 DEG C>The selectivity of olefin is reduced at 99%, so the optimum temperature is between 60 and 100 ℃.
TABLE 3 Experimental results data for catalysts prepared at different agitation temperatures for semi-hydrogenation reactions
Example 7
S1: taking Pd with the same molar mass4S/γ-Al2O3Dispersing in different organic solvents, introducing 1 hydrogen atmosphere of hydrogen gas for 10min, keeping the gas atmosphere, adding n-butylmercaptan as thiol ligand M to make the molar ratio of M to Pd 0.3: 1, stirring for 60min at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, vacuum filtering, drying for 12 hr to obtain M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. Table 4 shows the data of the results of the semi-hydrogenation reaction of different organic solvents for modifying thiol ligands, and the data can be analyzed to determine the modification process using DMF, acetonitrile, ethanolWhen the catalyst is used in a polar organic solvent, the prepared catalyst has higher selectivity on olefin, but the nonpolar organic solvent such as n-hexane has a much poorer effect, wherein DMF has the best modification effect as the solvent.
TABLE 4 data of experimental results of semi-hydrogenation reaction of thiol ligands modified by different organic solvents
Example 8
S1: pd with the same molar mass4Dispersing S/C in different DMF solvents, introducing hydrogen with 1 hydrogen atmosphere pressure for reaction for 10min, keeping the gas atmosphere, adding n-butylmercaptan as thiol ligand M to ensure that the molar ratio of M to Pd is 0.5: 1, stirring for 60min at 80 ℃, suction-filtering out the catalyst, washing with ultrapure water, suction-filtering, drying for 12h to obtain M-Pd4The S/C catalyst was kept ready (M is n-butylmercaptan).
S2: the prepared M-Pd4The S/C catalyst takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of alcohol solvent into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, ultrasonically dispersing for 1min, setting the temperature to be 20-80 ℃, adding a corresponding amount of catalyst, keeping the molar ratio of the substrate to pd to be (1000-4000) to 1, replacing 3 times of hydrogen, keeping 1-3bar of hydrogen in the reaction bottle, setting the rotating speed to be 1000rpm, and opening stirring. Table 5 shows the different experimental conditions and the results of the semi-hydrogenation reaction of the catalyst of the present invention. It can be seen that the catalyst of the present invention performs the semi-hydrogenation reaction and the alkyne conversion under different conditions>The selectivity of olefin can reach more than 98 percent when the content is 99 percent.
TABLE 5 different experimental conditions and the resulting data for the semi-hydrogenation reaction of the catalyst of the invention
Example 9
S1: pd with the same molar mass4S/γ-Al2O3Dispersing in DMF solvent, introducing 1 hydrogen gas at atmospheric pressure for reaction for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make molar ratio of M to Pd 0.4: 1, stirring for 60min at 100 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, vacuum filtering, drying for 12 hr to obtain M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst selects different intermediate alkyne compounds to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. TABLE 6M-Pd4S/γ-Al2O3Results of semi-hydrogenation experiments on different intermediate alkyne Compounds with catalysts, alkyne conversion>The selectivity of olefin can reach more than 98 percent when the content is 99 percent, and the M-Pd obtained by preparation can be seen4S/γ-Al2O3The catalyst has high selectivity for different intermediate alkyne compounds.
TABLE 6M-Pd obtained by the preparation4S/γ-Al2O3Data on experimental results of semi-hydrogenation reaction of catalyst for different intermediate alkyne compounds
Example 10
S1: pd with the same molar mass4S/γ-Al2O3Dispersing in DMF solvent, introducing 1 atmosphere of hydrogenReacting with hydrogen for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make the molar ratio of M to Pd 0.4: 1, stirring for 60min at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, vacuum filtering, drying for 12 hr, and making into M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst respectively takes the mixture of different alkenes and alkynes as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. Table 7 shows the data of the experiment results of the semi-hydrogenation reaction of the catalyst of the present invention on the mixture of olefins and alkynes, and it can be seen that the catalyst of the present invention has excellent catalytic activity and selectivity on the mixture of different olefins and alkynes, and the selectivity of the corresponding olefins is maintained above 98% for a long time.
TABLE 7 data of the results of the semi-hydrogenation reaction of the catalyst of the present invention on a mixture of alkenes and alkynes as substrates
Example 11
S1: pd with the same molar mass4S/γ-Al2O3Dispersing in DMF solvent, introducing hydrogen-containing gas, reacting for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make molar ratio of M to Pd 0.6: 1, stirring for 60min at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12 hr, and making into M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3CatalysisThe agent takes 1-phenyl-1-propyne as a substrate to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
Table 8 shows the results of the semi-hydrogenation reaction with the catalyst prepared according to the present invention, wherein the volume ratio of hydrogen to the protective gas is different from the pressure of the gas atmosphere, and it can be seen that when the hydrogen and the protective gas are mixed in the gas atmosphere in a volume ratio of 1: 0-4, and the conversion of 1-phenyl-1-propyne in the semi-hydrogenation reaction with the catalyst prepared according to the present invention is greater than 99%, the selectivity of olefin can reach more than 98%, wherein, when the volume content of hydrogen is 100%, the selectivity is the best; in addition, when the pressure of the gas atmosphere is 0.5-5 atmospheric pressures, the selectivity of olefin is good and can reach more than 98% when the catalyst prepared by the invention is used for carrying out the semi-hydrogenation reaction and the conversion of 1-phenyl-1-propyne is more than 99%.
TABLE 8 data of experimental results of semi-hydrogenation reactions with catalysts of the present invention prepared with different volume ratios of hydrogen and shielding gas and different pressures of the gas atmosphere
Comparative example 1
S1: selecting 1 percent Pd/gamma-Al in mass fraction2O3Dispersed in Na2In the aqueous solution of S, the mole ratio of Pd to S is 4: 1, the temperature is raised to 150 ℃, the reaction is carried out for 3 hours under the pressure of 1Mpa of hydrogen, and the Pd is obtained after cooling, suction filtration and drying4S/γ-Al2O3。
S2: prepared Pd4S/γ-Al2O3Dispersing in DMF solvent, introducing 1 hydrogen gas at atmospheric pressure, reacting for 10min, maintaining gas atmosphere, adding n-butylmercaptan as thiol ligand M to make molar ratio of M to Pd 0.4: 1, stirring for 60min at stirring temperatureFiltering out the catalyst at 80 ℃, washing and drying the catalyst for 12 hours by ultrapure water to prepare M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S3: Pd/gamma-Al2O3And Pd obtained by the preparation4S/γ-Al2O3And M-Pd4S/γ-Al2O3The catalysts are respectively used for carrying out semi-hydrogenation reaction by taking 1-phenyl-1-propyne as a substrate, and the reaction steps are as follows: 20ml of ethanol is taken and transferred into a reaction bottle with the diameter of 48m1, 2mmol of substrate is taken and put into the reaction bottle and ultrasonically dispersed for 1min, the temperature is set to be 60 ℃, a corresponding amount of catalyst is added, the molar ratio of the substrate to pd is 2000: 1, 1bar of hydrogen is kept in the reaction bottle after 3 times of hydrogen replacement, the rotation speed is set to be 1000rpm, and the stirring is turned on. TABLE 9 Pd/. gamma. -Al2O3、Pd4S/γ-Al2O3、M-Pd4S/γ-Al2O3The data of the catalyst semi-hydrogenation reaction experiment result are shown in FIG. 5, which is Pd/gamma-Al2O3Conversion and selectivity profiles for the semi-hydrogenation experiments, FIG. 6 is Pd4S/γ-Al2O3The conversion and selectivity profiles for the semi-hydrogenation experiments are shown in FIG. 7 for M-Pd4S/γ-Al2O3The catalyst is used for the conversion rate and the selectivity of a semi-hydrogenation experiment, and only M-Pd can be seen4S/γ-Al2O3The catalyst has high selectivity for semi-hydrogenation of intermediate alkyne compounds, and the selectivity is not derived from Pd only4S is not a modification of n-butylmercaptan but a result of the interaction of the two.
TABLE 9 Pd/γ -Al2O3、Pd4S/γ-Al2O3、M-Pd4S/γ-Al2O3Comparison of experimental result data of semi-hydrogenation reaction of catalyst
Comparative example 2
A first group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. 3, 4-Difluorophenylthiol was added to the mixture, which was then heated to 60 ℃ with stirring switched on at 1000rpm for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
Second group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. 3, 4-Difluorophenylthiol was added to the mixture and heated to 60 ℃ and after 3-fold replacement of hydrogen, 1bar of hydrogen was maintained in the reaction flask, the rotation speed was set at 1000rpm and stirring was switched on for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
Third group: 0.1g of Pd4S/C was dispersed in a high pressure glass vial in 5mL of DMF. 3, 4-Difluorophenylthiol was added to the mixture, which was then heated to 60 ℃ with stirring switched on at 1000rpm for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
And a fourth group: 0.1g of Pd4S/C was dispersed in a high pressure glass vial in 5mL of DMF. 3, 4-Difluorophenylthiol was added to the mixture and heated to 60 ℃ and after 3-fold replacement of hydrogen, 1bar of hydrogen was maintained in the reaction flask, the rotation speed was set at 1000rpm and stirring was switched on for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
The four groups of catalysts are used for hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
Table 10 presents the results of the semi-hydrogenation reaction performed on four groups of prepared catalysts. It can be seen that the catalysts prepared without introducing hydrogen during the modification have comparable activity but much poorer selectivity. Fig. 8 is an XRD pattern of the catalyst obtained in the first set of experiments, fig. 9 is an XRD pattern of the catalyst obtained in the second set of experiments, and fig. 10 is a transmission electron microscopy characterization transmission electron microscopy image of the catalyst prepared in the first set of experiments. We can see the first by transmission electron microscope in FIG. 10One group of catalyst part positions obtained by non-hydrogen preparation can see that the lattice fringe spacing corresponding to the crystalline phase of Pd4S is 0.228nm, but the corresponding XRD pattern contains Pd4The characteristic peak of S is essentially not visible, indicating that the catalyst obtained according to the first set of reaction conditions (absence of hydrogen) presents a very small portion of Pd although it does4S product, but Pd4The S yield is low and does not have a good crystal structure, and the second group is introduced with hydrogen to prepare Pd in the XRD pattern of the catalyst4The S characteristic peak is obvious. Likewise, the third set of reaction conditions (Pd) is compared to the first set of reaction conditions4S in no hydrogen condition) did not significantly improve the selectivity compared to the first set of experiments, under the fourth set of reaction conditions (Pd)4S in hydrogen) to obtain a catalyst with high selectivity for the intermediate alkyne hemihydrogenation. This is because stable Pd is produced in a hydrogen atmosphere4S crystal phase product and modifying with thiol ligand under hydrogen condition to obtain Pd modified with thiol ligand4The S catalyst has higher selectivity for intermediate alkyne hemihydrogenation, and the selectivity of olefin can reach more than 99 percent, which is breakthrough progress in the field of alkyne hemihydrogenation. The catalyst prepared without introducing hydrogen in the modification process can prepare a small amount of Pd4S, due to poor crystallinity of the product, and no further modification of thiol ligands under hydrogen conditions, but much worse than catalysts prepared by passing hydrogen. Therefore, the introduction of hydrogen in the process of preparing the catalyst can lead Pd4The S crystal phase is stable, and the ligand is better modified, so that the effect of high selectivity on olefin is achieved.
TABLE 10 data of experimental results of semi-hydrogenation reactions on catalysts prepared under different conditions
Comparative example 3
A first group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. N-butylmercaptan was added to the mixture, which was then heated to 60 ℃ and stirred for 12 hours with the rotation speed set at 1000rpm and the stirring switched on. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
Second group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. Mercaptoethanol was added to the mixture, which was then heated to 60 ℃ with setting of 1000rpm and turning on of the stirring, stirring for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
Third group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. N-butylmercaptan was added to the mixture and heated to 60 ℃ and after 3 hydrogen replacements 1bar of hydrogen was maintained in the reaction flask, set at 1000rpm and stirring was switched on for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
And a fourth group: 0.1g Pd/C was dispersed in a high pressure glass vial in 5mL DMF. Mercaptoethanol was added to the mixture and heated to 60 ℃ and after 3-fold replacement of hydrogen, 1bar of hydrogen was maintained in the reaction flask, the rotational speed was set at 1000rpm and stirring was switched on for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
The four groups of catalysts are used for semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. Table 11 below shows the data of the results of four different experiments performed on catalysts prepared under different conditions. It can be seen that the linear mercaptan modified Pd, with or without hydrogen, could not be used to prepare a high selectivity catalyst for the intermediate alkyne hemihydrogenation reaction because the C-S bond of the linear mercaptan was difficult to break and no Pd could be formed4S, and thus the linear thiol cannot be modified to have the effect of increasing the selectivity to the olefin.
TABLE 11 data of the results of semi-hydrogenation reactions in catalysts prepared under different experimental conditions
Comparative example 4
S1: pd with the same molar mass4S/γ-Al2O3Dispersing in DMF solvent, introducing 1 hydrogen gas at atmospheric pressure for reaction for 10min, keeping gas atmosphere, adding n-butylmercaptan as thiol ligand M to make molar ratio of M to Pd 0.4: 1, stirring for 60min at 80 deg.C, vacuum filtering to obtain catalyst, washing with ultrapure water, drying for 12 hr, and making into M-Pd4S/γ-Al2O3Catalyst is reserved (M is n-butylmercaptan).
S2: the prepared M-Pd4S/γ-Al2O3The catalyst respectively takes different terminal alkyne compounds as substrates to carry out semi-hydrogenation reaction, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. Table 12 shows the data of the experimental results of the semi-hydrogenation reaction of the catalyst of the present invention using different terminal alkyne compounds as substrates, and it can be seen that the semi-hydrogenation selectivity of the catalyst of the present invention to terminal alkyne compounds is low, and both of them are less than 80%, and therefore, the catalyst is not suitable for the semi-hydrogenation reaction of terminal alkyne compounds.
TABLE 12 data of experimental results of semi-hydrogenation reactions of catalysts of the invention with different terminal alkyne compounds as substrates
Comparative example 5
S1: Pd/gamma-Al with the mass fraction of Pd of 1 percent2O3Dispersed in different amounts of Na2Heating to 150 ℃ in the S aqueous solution, reacting for 3h under the pressure of 1Mpa of hydrogen, cooling, filtering, and drying to obtain PdxSy/gamma-Al2O3。
S2: mole of PdPdxSy/gamma-Al with same mass2O3Dispersing in DMF solvent, introducing hydrogen with one hydrogen atmosphere pressure for reaction for 10min, keeping the gas atmosphere, adding n-butylmercaptan as thiol ligand M to ensure that the molar ratio of M to Pd is 0.4: 1, stirring for 12h at the stirring temperature of 80 ℃, leaching out the catalyst, washing with ultrapure water and drying for 12h to obtain catalyst A, catalyst B and catalyst C for later use.
S3: carrying out semi-hydrogenation reaction on the prepared catalyst A, catalyst B and catalyst C by taking 1-phenyl-1-propyne as a substrate, wherein the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring. Table 13 shows the data of the results of semi-hydrogenation reactions performed on the catalysts of the present invention prepared in different crystal forms of PdxSy, from which Pd was obtained4S as PdS phase with lowest sulfur content, the catalyst prepared from S has highest activity, and Pd4S can more easily accept a thiol ligand, and the prepared catalyst has the highest selectivity on olefin.
TABLE 13 preparation of crystalline forms of PdxSy the data of the results of the semi-hydrogenation reaction of the catalysts of the invention
Comparative example 6
S1: palladium is typically treated with a sulfur-containing compound: the sulfur-containing compound is used for processing Pd to obtain Pd and a reactant of the sulfur-containing compound.
S2: reduction reaction: heating to 150 deg.C, and reacting at 1: 1 ratio of H2∶N2Reduction in stream (100mL/min) for 1 hour, followed by N2Cooling in the flow to prepare the reduced palladium catalyst.
S3: second treatment of the palladium with a sulfur-containing compound: the reduced palladium catalyst was added to 100mL of a solution of hexane and a sulfur-containing compound, wherein the molar ratio of the sulfur-containing compound to Pd, as measured by the bulk Pd metal content, was 2.5: 1, stirred for 30min, and the solvent was evaporated on a rotary evaporator to prepare the catalyst for use.
S4: and (3) testing the effect: the prepared catalyst is subjected to semi-hydrogenation reaction by taking 1-phenyl-1 propyne as a substrate, and the reaction steps are as follows: transferring 20ml of ethanol into a 48ml reaction bottle, putting 2mmol of substrate into the reaction bottle, performing ultrasonic dispersion for 1min, setting the temperature at 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing 3 times of hydrogen, keeping 1bar of hydrogen in the reaction bottle, setting the rotation speed at 1000rpm, and turning on stirring.
Table 14 shows the data of the results of the semi-hydrogenation experiments performed on the catalysts prepared by treating palladium with different sulfur-containing compounds, and it can be seen that the catalysts prepared by the method have selectivity for semi-hydrogenation of alkyne, but the selectivity is not high, and both the selectivity and the selectivity are less than 80%, which is far less than the effect achieved by the catalysts of the present invention, and the catalysts are not suitable for selective semi-hydrogenation of intermediate alkyne compounds.
TABLE 14 data of experimental results of semi-hydrogenation of catalysts prepared by treating palladium with different sulfur-containing compounds
Comparative example 7
S1: prepared Pd4S/γ-Al2O3Dispersing in DMF solvent, introducing hydrogen with 1 hydrogen atmosphere pressure for reaction for 10min, keeping the gas atmosphere, adding thiourea as a ligand to ensure that the molar ratio of thiourea to Pd is 0.4: 1, stirring for 60min at the stirring temperature of 80 ℃, leaching out the catalyst, washing and drying with ultrapure water for 12h, and preparing the catalyst A for later use.
S2: respectively adding Pd with the same molar mass4S/γ-Al2O3Respectively carrying out semi-hydrogenation reaction by using 1-phenyl-1-propyne as a substrate by using the prepared catalyst A, wherein the reaction steps are as follows: 20ml of ethanol are transferred into a 48ml reaction flask, and 2mmol of substrate are takenPlacing into a reaction bottle, ultrasonically dispersing for 1min, setting the temperature to be 60 ℃, adding a corresponding amount of catalyst, wherein the molar ratio of the substrate to pd is 2000: 1, replacing hydrogen for 3 times, keeping 1bar of hydrogen in the reaction bottle, setting the rotating speed to be 1000rpm, and opening stirring. TABLE 15 Pd4S/γ-Al2O3And the catalyst A carries out semi-hydrogenation reaction experiment result data. As can be seen from the data in the table, thiourea as a ligand did not improve the selectivity towards olefins.
TABLE 15 Pd4S/γ-Al2O3thiourea-Pd4S/γ-Al2O3Data of experimental results of carrying out semi-hydrogenation reaction
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (6)
1. A catalyst modified by thiol ligand is characterized in that the general formula of the catalyst is M-Pd4S or M-Pd4S/X; m is a thiol ligand and is used for modifying Pd4S; the X is a carrier;
the catalyst is prepared by reacting Pd4S or Pd4Dispersing S/X in polar organic solvent, introducing hydrogen-containing gas and maintaining gas atmosphere, adding thiol ligand M, stirring, vacuum filtering, and drying to obtain M-Pd4S catalyst or M-Pd4An S/X catalyst;
the polar organic solvent is at least one selected from DMF, acetonitrile and alcohol solvent;
the stirring temperature is 50-120 ℃;
the thiol ligand is selected from at least one of linear thiol and aromatic thiophenol;
the linear mercaptan is selected from at least one of n-butyl mercaptan, thioglycolic acid, n-hexyl mercaptan, 1-octyl mercaptan and dodecyl mercaptan; the aromatic thiophenol is at least one selected from thiophenol, 3, 4-difluorothiophenol, 1-chlorothiophenol, 3, 4-dimethylthiophenol and 4-tert-butylthiophenol.
2. The catalyst of claim 1, wherein the gas atmosphere consists of hydrogen and a protective gas in a volume ratio of 1 (0-4), and the pressure of the gas atmosphere is 0.5-5 atm.
3. The catalyst according to claim 1, wherein the molar ratio of thiol ligand M to Pd is (0.02-1.1): 1.
4. Use of a catalyst according to any one of claims 1 to 3 in the hemihydrogenation of an intermediate alkyne compound.
5. The use according to claim 4, wherein the intermediate alkyne compound is selected from at least one of 1-phenyl-1-propyne, 1-phenyl-1-pentyne, tolane, 4-phenyl-3-butyn-2-one, 4-octyne, 3-phenyl-2-propyne-1-ol, and methyl phenylpropionate.
6. The use according to claim 4, wherein the molar ratio of the intermediate alkyne compound to Pd is (1000-4000): 1.
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