WO2022012005A1 - 一种用硫醇类配体修饰的催化剂及其制备方法与应用 - Google Patents

一种用硫醇类配体修饰的催化剂及其制备方法与应用 Download PDF

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WO2022012005A1
WO2022012005A1 PCT/CN2021/071075 CN2021071075W WO2022012005A1 WO 2022012005 A1 WO2022012005 A1 WO 2022012005A1 CN 2021071075 W CN2021071075 W CN 2021071075W WO 2022012005 A1 WO2022012005 A1 WO 2022012005A1
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catalyst
hydrogen
semi
hydrogenation
reaction
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郑南峰
李志恺
刘圣杰
陈洁
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Xiamen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Definitions

  • the present invention relates to a catalyst, especially a catalyst modified with a thiol ligand and a preparation method and application thereof.
  • alkynes are mainly divided into two categories, terminal alkynes and intermediate alkynes, especially the selective hydrogenation of internal alkynes in fine chemical synthesis, pharmaceutical synthesis, health care product development and agricultural use.
  • the synthesis of chemicals all play an important role in catalysis. In order to obtain high yields of target products and make the reaction process economical, energy-saving and environmentally friendly, the development of sustainable catalysts has attracted great attention.
  • metal poisoning In traditional industrial applications, in order to improve product selectivity, highly active metals are generally selectively protected by organic or inorganic substances, a strategy called "metal poisoning". In general, there are two strategies for poisoning by selective hydrogenation: (1) Synthesis of multimetallic nanomaterials that generate electronic effects that affect the adsorption of reactants or products; for example, for gas-phase acetylene hydrogenation, industrial catalysts generally Using Pd-Ag, Pd-Au, Pd-Bi, Pd-Cu, Pd-Ga, PdSn, Pd-Zn, etc., for the hydrogenation of nitro compounds, Pb, V or other Pb, V or other Pt-containing compounds are generally modified on Pt.
  • N S or Cl compounds and catalysts such as Pt-Cr, Pt-Mn, Pt-Fe, Pt-Co, Pt-Ni, Pt-Au, Pt-Pd, Pt-Zn, Pt-Pb, Pt-V ;
  • catalysts such as Pt-Cr, Pt-Mn, Pt-Fe, Pt-Co, Pt-Ni, Pt-Au, Pt-Pd, Pt-Zn, Pt-Pb, Pt-V ;
  • catalysts such as Pt-Cr, Pt-Mn, Pt-Fe, Pt-Co, Pt-Ni, Pt-Au, Pt-Pd, Pt-Zn, Pt-Pb, Pt-V ;
  • Surface modification of metal nanoparticles to generate metal-ligand interactions and then affect the selectivity of catalysts For example, for the hydrogenation of alkynes in the liquid phase, Pd/CaCO 3 whose surface is poisone
  • Patent CN101428228A discloses a selective hydrogenation catalyst, wherein the active components of the catalyst are palladium and auxiliary copper, and alumina is used as a carrier. The catalyst is suitable for selective hydrogenation and removal of alkynes rich in alkyne residues.
  • Patents CN1176291 and CN102688783A respectively use honeycomb material and alumina silicon carbide as the carrier, both use palladium as the active main component, and alkali metals and alkaline earth metals as auxiliary agents to achieve high selectivity for semi-hydrogenation of alkynes, but these are aimed at The selective semi-hydrogenation of terminal alkynes in petroleum cracking in the petrochemical field is not the selective semi-hydrogenation of intermediate alkynes.
  • the selectivity is generally attributed to electronic effects brought about by changes in the metal surrounding environment and steric hindrance effects brought about by surface modifications. Due to the high activity of palladium, the traditional method often needs to poison some sites in order to have good selectivity to alkynes, which leads to low catalyst activity and increases the use of precious metals, thereby increasing the cost; another On the one hand, the method for preparing the selective hydrogenation catalyst is relatively complicated, especially the method for the catalyst that only performs the semi-hydrogenation reaction on the intermediate alkyne is difficult to be applied and produced on an industrial scale.
  • the preparation of an excellent catalyst with intermediate alkyne-selective semi-hydrogenation activity can make full use of the active center of the catalyst to improve the activity of the reaction, and at the same time, the operation is simple and convenient, which is beneficial to reduce the preparation cost of the catalyst, which is of great significance for industrial application. and value.
  • An object of the present invention is to solve the existing problems and provide a catalyst.
  • Another object of the present invention is to provide a method for preparing a catalyst.
  • Another object of the present invention is to provide a catalyst application.
  • the present invention adopts following technical scheme:
  • a first aspect of the present invention provides a catalyst modified with a thiol ligand, the general formula of the catalyst is M-Pd 4 S or M-Pd 4 S/X; the M is a thiol ligand, which is For the modification of Pd 4 S; the X is a carrier.
  • the carrier X is selected from at least one of C, CaCO 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , cerium oxide, molecular sieve, silicon oxide, titanium oxide and diatomaceous earth.
  • the thiol ligand M is selected from at least one of linear thiols and aromatic thiophenols.
  • the straight-chain thiol is selected from at least one of n-butanethiol, thioglycolic acid, n-hexanethiol, 1-octanethiol and dodecanethiol;
  • the aromatic thiophenol is selected from thiophenol , at least one of 3,4-difluorothiophenol, 1-chlorothiophenol, 3,4-dimethylthiophenol and 4-tert-butylthiophenol.
  • a second aspect of the present invention provides a method for preparing a catalyst modified with a thiol ligand, comprising the following steps:
  • Disperse Pd 4 S or Pd 4 S/X in a polar organic solvent pass in a hydrogen-containing gas and keep the gas atmosphere, add thiol ligand M, stir, filter with suction, and dry to obtain M-Pd 4 S catalyst or M-Pd 4 S/X catalyst.
  • the polar organic solvent is selected from at least one of DMF, acetonitrile and alcohol solvents.
  • the hydrogen-containing gas atmosphere is composed of hydrogen and protective gas in a volume ratio of 1:(0-4), and the pressure of the gas atmosphere is 0.5-5 atmospheres, and further preferably, hydrogen and protective gas by volume The ratio is 1:(0-1), and the protective gas is selected from one of Ar and N 2 .
  • the molar ratio of the thiol ligand M:Pd is (0.02-1.1):1.
  • the molar ratio of the thiol ligand M:Pd is (0.1-0.8):1.
  • the stirring time is 10min-12h.
  • the stirring temperature is 50-120°C.
  • the temperature of the stirring is 60-100°C.
  • the third aspect of the present invention also provides an application of the catalyst obtained by the above catalyst or the above preparation method, in the semi-hydrogenation of an intermediate alkyne compound.
  • the intermediate alkyne compound is selected from 1-phenyl-1-propyne, 1-phenyl-1-pentyne, diphenylacetylene, 4-phenyl-3-butyn-2-one, 4-octyne At least one of alkyne, 3-phenyl-2-propyn-1-ol and methyl phenylpropynoate.
  • the molar ratio of the intermediate alkyne compound to Pd is (1000-4000):1.
  • a catalyst is applied to a method for the semi-hydrogenation of an intermediate alkyne compound, comprising the following steps:
  • the polar organic solvent is transferred to the reaction flask, the intermediate alkyne compound is selected as the substrate and placed in the reaction flask to disperse, the temperature is set to 20-80 ° C, the catalyst of the present invention is added, and the mol ratio of the substrate to Pd is (1000-4000 ): 1, replace the hydrogen, keep the hydrogen pressure of 1-3 atmospheres, and stir.
  • the hydrogenation of alkynes is generally divided into two steps of hydrogenation, the first step of hydrogenation of alkynes to generate alkenes, and then the further hydrogenation of alkenes to generate alkanes, the semi-hydrogenation of alkynes in the present invention refers to the first step of alkynes
  • the process of hydrogenating hydrocarbons to olefins is called semi-hydrogenation of alkynes.
  • Chemical modification refers to attaching active groups or catalytic substances to the surface of the modified object by methods such as adsorption, coating, polymerization, and chemical reaction.
  • Pd 4 S can be selected from nanoscale materials, and its morphology includes but is not limited to particle, flake, and rod.
  • a large sterically hindered ligand is modified to Pd 4 S or Pd 4 S/X to realize the adsorption of alkynes and the desorption of alkenes to achieve high selectivity of alkenes.
  • the prepared catalyst After modifying thiol ligands with Pd 4 S or Pd 4 S/X in a hydrogen-containing gas atmosphere, the prepared catalyst has high selectivity for the semi-hydrogenation of intermediate alkyne compounds, and the selectivity can reach 97% or more.
  • the catalyst of the present invention has a high conversion rate for the semi-hydrogenation reaction of the intermediate alkyne compound, and the conversion rate can reach more than 99%.
  • the catalyst prepared by the present invention has high stability, and is not significantly deactivated after repeated application, and the selectivity can still reach more than 98% after repeated application.
  • the amount of modified thiol ligands used in preparing the catalyst of the present invention is small, the price is low, the reproducibility and stability are good, and the cost is reduced, which is beneficial to industrial application.
  • the preparation method of the catalyst of the present invention is simple in operation, simple in process and universal.
  • Fig. 1 (a) is the conversion rate and selectivity curve diagram of PdNs in embodiment 1 using 1-phenyl-1-propyne as substrate to carry out semi-hydrogenation reaction;
  • Figure 1(b) is a graph showing the conversion rate and selectivity of the semi-hydrogenation reaction of Pd 4 S Ns using 1-phenyl-1-propyne as a substrate in Example 1;
  • Figure 1(c) is the conversion rate and selectivity curve of the semi-hydrogenation reaction of M-Pd 4 S Ns catalyst with 1-phenyl-1-propyne as the substrate in Example 1 (M is n-butanethiol) ).
  • Fig. 2 is the infrared spectrum before and after modification of n-butanethiol in Example 2, (1) is the peak of n-butyl that appears after modification of n-butanethiol.
  • FIG. 3 is a chromatogram of the detection of products by gas chromatography by sampling at regular intervals in Example 2.
  • Example 4 is a graph showing the results of the cycle stability experiment of the M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst in Example 3 in which the semi-hydrogenation reaction experiment was applied 8 times (M is n-butanethiol).
  • FIG. 5 is a graph showing the conversion and selectivity of Pd/ ⁇ -Al 2 O 3 used in the semi-hydrogenation experiment in Comparative Example 1.
  • FIG. 5 is a graph showing the conversion and selectivity of Pd/ ⁇ -Al 2 O 3 used in the semi-hydrogenation experiment in Comparative Example 1.
  • FIG. 6 is a graph showing the conversion and selectivity of Pd 4 S/ ⁇ -Al 2 O 3 used in the semi-hydrogenation experiment in Comparative Example 1.
  • FIG. 6 is a graph showing the conversion and selectivity of Pd 4 S/ ⁇ -Al 2 O 3 used in the semi-hydrogenation experiment in Comparative Example 1.
  • FIG. 8 is the XRD pattern of the catalyst obtained in the first set of experiments in Comparative Example 2.
  • FIG. 9 is the XRD pattern of the catalyst obtained in the second set of experiments in Comparative Example 2.
  • Figure 10 is a TEM image of the catalysts prepared in the first group of experiments in Comparative Example 2 being characterized by TEM.
  • Figure 1 shows the conversion and selectivity curves of (a) Pd Ns, (b) Pd 4 S Ns and (c) M-Pd 4 S Ns catalysts for the semi-hydrogenation of 1-phenyl-1-propyne .
  • Example 3 Stability of the catalyst of the present invention applied mechanically
  • Figure 4 shows the results of the cycle stability experiment of the M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst for 8 times of semi-hydrogenation experiments.
  • the conversion rate and selectivity curves are shown in Figure 4. It can be seen that this After the catalyst of the invention is applied 8 times, the selectivity still reaches more than 98%, and the stability is good.
  • the Pd/X with the same Pd molar mass and the prepared M-Pd 4 S/X catalyst are respectively used for the semi-hydrogenation reaction with 1-phenyl-1-propyne as the substrate.
  • the reaction steps are: take 20 ml of Ethanol was transferred to a 48ml reaction flask, 2 mmol of substrate was put into the reaction flask and ultrasonically dispersed for 1 min, the temperature was set to 60°C, a corresponding amount of catalyst was added, the molar ratio of substrate to pd was 2000:1, and the hydrogen was replaced 3 times. After keeping 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on the stirring.
  • Table 1 is a data table of the experimental results of the semi-hydrogenation reaction of catalysts prepared with different supports. It can be seen that the selectivity of the catalysts prepared by the preparation method of the present invention for the semi-hydrogenation reaction with different supports is above 98%, and all have high selectivity for the semi-hydrogenation reaction. of selectivity.
  • the carrier can also be molecular sieve, silicon oxide, titanium oxide and diatomaceous earth.
  • the prepared M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst is subjected to a semi-hydrogenation reaction with 1-phenyl-1-propyne as a substrate.
  • the reaction steps are: take 20ml of ethanol and transfer it to 48ml of ethanol In the reaction flask, take 2 mmol of the substrate, put it into the reaction flask and disperse it ultrasonically for 1 min, set the temperature to 60 °C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, replace the hydrogen for 3 times and keep it in the reaction flask. With 1 bar of hydrogen, set the speed to 1000 rpm and turn on stirring.
  • the selectivity of alkenes is higher when the conversion of alkynes is >99%, All reached more than 98%, and the optimal range of thiol ligand dosage was between (0.1-0.8):1.
  • the stirring time also has a certain influence. When the stirring time is 10min-12h, the alkene selectivity reaches more than 98% when the alkyne conversion is >99%, which is the best range.
  • Table 3 shows the experimental data of the M-Pd 4 S/ ⁇ -Al 2 O 3 catalysts prepared at different stirring temperatures for the semi-hydrogenation reaction. It can be seen that when the stirring temperature is 50-120 ° C, the alkyne When the conversion is >99%, the selectivity of olefins reaches more than 98%. When the stirring temperature is less than 60 °C, and when the stirring temperature is greater than 100 °C, the selectivity of alkenes decreases when the conversion of alkynes is more than 99%. Therefore, The optimum temperature is between 60-100°C.
  • Table 4 is the experimental result data that different organic solvents are used to modify thiol ligands for semi-hydrogenation reaction. From the data, it can be analyzed that when the solvents in the modification process are polar organic solvents such as DMF, acetonitrile and ethanol, the prepared catalysts The selectivity for olefins is higher, while the effect of using non-polar organic solvents such as n-hexane is much worse, and the modification effect of DMF as a solvent is the best.
  • polar organic solvents such as DMF, acetonitrile and ethanol
  • the prepared M-Pd 4 S/C catalyst is subjected to a semi-hydrogenation reaction with 1-phenyl-1-propyne as a substrate.
  • the reaction step is: take 20ml of alcohol solvent and transfer it to a 48ml reaction flask , take 2 mmol of substrate and put it into the reaction bottle and disperse it ultrasonically for 1min, set the temperature to 20-80 °C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is (1000-4000): 1, and keep it after replacing 3 times of hydrogen There is 1-3 bar of hydrogen in the reaction flask, the speed is set to 1000 rpm and the stirring is turned on.
  • Table 5 is the different experimental conditions and the result data of the catalyst of the present invention to carry out the semi-hydrogenation reaction. It can be seen that the catalyst of the present invention performs the semi-hydrogenation reaction under different conditions, and the selectivity of alkenes can reach more than 98% when the conversion of alkynes is more than 99%.
  • the prepared M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst is used for the semi-hydrogenation reaction with different intermediate alkyne compounds.
  • the reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction flask, take 2mmol bottom Put the substance into the reaction bottle and ultrasonically disperse it for 1min, set the temperature to 60°C, add a corresponding amount of catalyst, and the molar ratio of substrate to pd is 2000:1. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction bottle, and set the rotation speed. to 1000 rpm and turn on stirring.
  • Table 6 shows the experimental results of the semi-hydrogenation of M-Pd 4 S/ ⁇ -Al 2 O 3 catalysts for different intermediate alkyne compounds. When the conversion of alkynes is more than 99%, the selectivity of alkenes can reach more than 98%. It can be seen that the preparation The obtained M-Pd 4 S/ ⁇ -Al 2 O 3 catalysts have high selectivity for different intermediate alkynes.
  • the prepared M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst is used for the semi-hydrogenation reaction with the mixture of different alkenes and alkynes as substrates.
  • the reaction steps are: take 20ml of ethanol and transfer it to 48ml of reaction In the bottle, take 2 mmol of substrate and put it into the reaction bottle and disperse it ultrasonically for 1 min, set the temperature to 60 °C, add a corresponding amount of catalyst, and the molar ratio of substrate to pd is 2000:1.
  • 1 bar of hydrogen set the speed to 1000 rpm and turn on the agitation.
  • Table 7 is the experimental data of the semi-hydrogenation reaction of the catalyst of the present invention on the mixture of alkene and alkyne. It can be seen that the catalyst of the present invention has excellent catalytic activity and selectivity for the mixture of different alkenes and alkynes, and the selectivity of the corresponding alkene is long. The time remained above 98%.
  • Table 8 prepares the experimental result data that catalyst of the present invention carries out semi-hydrogenation reaction that the volume ratio of hydrogen and protective gas is different from the pressure of gas atmosphere, and it can be seen that in the gas atmosphere, hydrogen and protective gas are in a volume ratio of 1:(0-4 ) composition, when the catalyst of the present invention is prepared for semi-hydrogenation reaction 1-phenyl-1-propyne conversion >99%, the selectivity of olefins can reach more than 98%, wherein, when the hydrogen volume content is 100%, the selectivity The effect is the best; in addition, when the pressure of the gas atmosphere is 0.5-5 atmospheres, when the catalyst of the present invention is prepared for semi-hydrogenation reaction 1-phenyl-1-propyne conversion > 99%, the selectivity of olefins is good, which can reach more than 98%. Table 8. Different volume ratios of hydrogen and protective gas and different pressures of gas atmosphere to prepare the catalyst of the present invention and carry out the experimental result data of semi-hydrogenation reaction
  • Table 9 shows the experimental data of the semi-hydrogenation reaction of Pd/ ⁇ -Al 2 O 3 , Pd 4 S/ ⁇ -Al 2 O 3 , M-Pd 4 S/ ⁇ -Al 2 O 3 catalysts, and Fig. 5 shows Pd/ ⁇ -Al 2 O 3
  • Fig. 6 is the conversion rate and selectivity curve of Pd 4 S/ ⁇ -Al 2 O 3 used in the semi-hydrogenation experiment
  • Group 1 Disperse 0.1 g Pd/C in a high pressure glass bottle in 5 mL DMF. 3,4-difluorothiophenol was added to the mixture, then heated to 60° C., set the rotational speed to 1000 rpm and turned on stirring, and stirred for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • the second group Disperse 0.1g Pd/C in a high pressure glass bottle in 5mL DMF. Add 3,4-difluorothiophenol to the mixture and heat it to 60°C. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotating speed to 1000 rpm and turn on stirring for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • Group 3 Disperse 0.1 g of Pd 4 S/C in a high pressure glass bottle in 5 mL of DMF. 3,4-difluorothiophenol was added to the mixture, then heated to 60° C., set the rotational speed to 1000 rpm and turned on stirring, and stirred for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • Group 4 Disperse 0.1 g of Pd 4 S/C in a high pressure glass bottle in 5 mL of DMF. 3,4 difluorothiophenol was added to the mixture and heated to 60°C. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on stirring 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 obtained were used for the hydrogenation reaction, and the reaction steps were as follows: take 20 ml of ethanol and transfer it to a 48 ml reaction flask, take 2 mmol of the substrate and put it into the reaction flask and ultrasonically disperse it for 1 min, set the temperature to 60 ° C, add the corresponding Amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on stirring.
  • Table 10 is the experimental result data of four groups of catalysts prepared for semi-hydrogenation reaction. It can be seen that the activity of the catalyst prepared without introducing hydrogen during the modification process is not much different, but the selectivity is much worse.
  • FIG. 8 is the XRD pattern of the catalyst obtained in the first group of experiments
  • FIG. 9 is the XRD pattern of the catalyst obtained in the second group of experiments
  • FIG. 10 is the transmission electron microscope pattern of the catalyst prepared in the first group of experiments.
  • the third set of reaction conditions did not significantly improve the selectivity compared to the first set of experimental conditions
  • the fourth set of reaction conditions Pd 4 S In hydrogen conditions
  • the obtained catalysts are highly selective for intermediate alkyne semi-hydrogenation. This is because a stable Pd 4 S crystalline product will be produced under a hydrogen atmosphere , and a thiol ligand-modified Pd 4 S catalyst can be obtained by modifying it with a thiol ligand under a hydrogen atmosphere.
  • the selectivity of hydrogen is higher, and the selectivity of alkenes can reach more than 99%, which is a breakthrough in the field of alkyne semi-hydrogenation.
  • the catalyst prepared without introducing hydrogen in the modification process can produce a small amount of Pd 4 S, due to the poor crystallinity of the product and no further modification of thiol ligands under the condition of hydrogen, it is incompatible with the catalyst prepared by introducing hydrogen. Much worse. Therefore, the introduction of hydrogen in the process of preparing the catalyst can stabilize the Pd 4 S crystal phase and improve the modification of the ligands, which has the effect of high selectivity to olefins.
  • Group 1 Disperse 0.1 g Pd/C in a high pressure glass bottle in 5 mL DMF. n-Butanethiol was added to the mixture, which was then heated to 60° C., set the rotational speed to 1000 rpm and turned on stirring, and stirred for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • the second group Disperse 0.1g Pd/C in a high pressure glass bottle in 5mL DMF.
  • the mercaptoethanol was added to the mixture, then heated to 60° C., the rotational speed was set to 1000 rpm and the stirring was turned on, and stirred for 12 hours.
  • the product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • the third group Disperse 0.1g Pd/C in a high pressure glass bottle in 5mL DMF. n-Butanethiol was added to the mixture and heated to 60°C. After 3 times of hydrogen replacement, 1 bar of hydrogen was maintained in the reaction flask. The rotating speed was set to 1000 rpm and the stirring was turned on for 12 hours. The product was collected by centrifugation with acetone. The product was dispersed in ethanol for further use.
  • Group 4 Disperse 0.1 g Pd/C in a high pressure glass bottle in 5 mL DMF. Add mercaptoethanol to the mixture and heat it to 60°C. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on stirring 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 obtained were used for the semi-hydrogenation reaction, and the reaction steps were as follows: take 20ml of ethanol and transfer it to a 48ml reaction flask; A corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on stirring.
  • Table 11 below is the experimental result data of four groups of catalysts prepared under different experimental conditions for semi-hydrogenation reaction.
  • the prepared M-Pd 4 S/ ⁇ -Al 2 O 3 catalyst is used for semi-hydrogenation reaction with different terminal alkyne compounds as substrates.
  • the reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction flask, Take 2 mmol of the substrate and put it into the reaction flask and disperse it ultrasonically for 1 min, set the temperature to 60°C, add a corresponding amount of catalyst, and the molar ratio of substrate to pd is 2000:1. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask. , set the speed to 1000 rpm and turn on stirring.
  • Table 12 shows the experimental data of the semi-hydrogenation reaction of the catalyst of the present invention using different terminal alkyne compounds as substrates. It can be seen that the semi-hydrogenation selectivity of the catalyst of the present invention to terminal alkyne compounds is low, all less than 80%, so it is not applicable In the semi-hydrogenation reaction of terminal alkyne compounds.
  • the prepared catalyst A, catalyst B, and catalyst C are subjected to a semi-hydrogenation reaction with 1-phenyl-1-propyne as a substrate, and the reaction step is: take 20ml of ethanol and transfer it to a 48ml reaction bottle, take the 2 mmol of the substrate was placed in the reaction flask and dispersed by ultrasonic for 1 min, the temperature was set to 60°C, a corresponding amount of catalyst was added, and the molar ratio of substrate to pd was 2000:1. After replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, Set the rotational speed to 1000 rpm and turn on agitation.
  • Table 13 shows the experimental data of the semi-hydrogenation reaction of the catalyst of the present invention prepared by different crystal forms of PdxSy, from which it is obtained that Pd 4 S, as the PdS phase with the lowest sulfur content, has the highest activity of the prepared catalyst, and Pd 4 S is more active. It readily accepts thiol ligands, and the prepared catalysts have the highest selectivity to olefins.
  • S1 General Treatment of Palladium with Sulfur-Containing Compounds: Treatment of Pd with sulfur-containing compounds results in a reactant of Pd and sulfur-containing compounds.
  • Test effect The prepared catalyst is subjected to a semi-hydrogenation reaction with 1-phenyl-1 propyne as the substrate.
  • the reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction bottle, take 2mmol of the substrate and put it in In the reaction flask and ultrasonically dispersed for 1min, set the temperature to 60 ° C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction flask, set the rotating speed to 1000rpm and Turn on stirring.
  • Table 14 is the experimental data of the semi-hydrogenation of the catalyst prepared by treating palladium with different sulfur-containing compounds. It can be seen that the catalyst prepared by this method is used for the semi-hydrogenation reaction. It has selectivity for the semi-hydrogenation of alkynes, but the selectivity is not It is not suitable for the selective semi-hydrogenation reaction of intermediate alkyne compounds.
  • reaction steps are as follows: Take 20ml of ethanol and transfer it to a 48ml reaction flask, take 2mmol of the substrate and put it into the reaction flask and disperse it ultrasonically for 1min, set the temperature to 60°C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, replace After 3 times of hydrogen, keep 1 bar of hydrogen in the reaction flask, set the rotation speed to 1000 rpm and turn on the stirring.
  • Table 15 shows the experimental data of the semi-hydrogenation reaction of Pd 4 S/ ⁇ -Al 2 O 3 and catalyst A. It can be seen from the data in the table that thiourea as a ligand cannot improve the selectivity to olefins.

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Abstract

本发明提出一种用硫醇类配体修饰的催化剂及其制备方法与应用，通入含氢气的气体并保持气体氛围下利用硫醇类配体修饰Pd 4S或Pd 4S/X，制备得到M-Pd 4S催化剂或带有载体的M-Pd 4S/X催化剂，利用本发明制备所得催化剂实现在炔烃半加氢反应中对中间炔化合物具有高选择性，同时，本发明催化剂的制备方法操作简单，具有普适性。

Description

一种用硫醇类配体修饰的催化剂及其制备方法与应用
技术领域：本发明涉及一种催化剂，特别是一种用硫醇类配体修饰的催化剂及其制备方法与应用。
背景技术：
炔烃选择性氢化在工业生产中的地位举足轻重，炔烃主要分为两大种类，端炔和中间炔，尤其是内炔的选择性氢化在精细化学品合成、药物合成、保健品开发以及农用化学品的合成方面都起着重要的作用在催化方面，为了得到高产率的目标产物，并使反应过程经济实用、节能且环境友好，发展可持续的催化剂引起了人们极大的关注。
传统的在工业应用上，为了提高产物的选择性，高活性的金属一般会选择性地被有机物或无机物保护住，这种策略被称作“金属的毒化”。一般来说，选择性氢化的毒化有两种策略：(1)合成多金属的纳米材料，产生电子效应从而影响反应物或产物的吸附；例如，对于气相的乙炔氢化反应来说，工业催化剂一般用Pd-Ag、Pd-Au、Pd-Bi、Pd-Cu、Pd-Ga、PdSn、Pd-Zn等，对于硝基类化合物的氢化，一般在Pt上修饰Pb、V或是其他一些含有P、N、S或Cl的化合物以及Pt-Cr、Pt-Mn、Pt-Fe、Pt-Co、Pt-Ni、Pt-Au、Pt-Pd、Pt-Zn、Pt-Pb、Pt-V等催化剂；(2)对金属纳米颗粒进行表面修饰，产生金属-配体相互作用然后影响催化剂的选择性。例如，对于液相的炔烃氢化，一般采用表面被Pb和喹啉毒化的Pd/CaCO 3，即Lindlar催化剂。AYan,Ning等(Pd-Pb alloy nano crystals with tailored composition for semihydrogenation:taking advantage of catalyst poisoning.W.X Niu,Y.J.Gao,W.Q.Zhang,N.Yan,X.M.Lu.Angew.Chem.Int.Ed.2015,127,8389-8392.)通过种子法制备了Pd-Pb纳米晶催化剂，通过Pb对Pd表面的毒化作用，使得这种催化剂在对苯乙炔有较好的选择性，但是Pb的毒化作用使得Pd-Pb催化剂的加氢活性变得很差。专利CN101428228A公开了一种选择性加氢催化剂，其中催化剂的活性组分钯、助剂铜，以氧化铝为载体，催化剂适用富含炔烃残余物的选择性加氢除炔，其载体处理和制备需要900℃以上的高温来处理。专利CN1176291和CN102688783A分别以蜂窝材料、氧化铝碳化硅为载体，都用钯做活性主分，碱金属与碱土金属做助剂，实现对炔烃半加氢的高 选择性，但是这些都是针对于石油化工领域石油裂解时出现的端炔的选择性半氢化，都不是中间炔的选择性半氢化。
对于多相催化剂来说，选择性一般归因于金属周围环境变化带来的电子效应以及表面修饰物带来的位阻效应。由于钯的活性高，传统的做法往往需要毒化部分的位点，才能对炔烃有好的选择性，这就导致了催化剂的活性很低，增加了贵金属的使用，从而增加了成本；另一方面，选择性加氢催化剂制备的方法较为复杂，特别是只对中间炔进行半加氢反应的催化剂的方法较难进行工业规模的应用生产。因此，制备优异的具有中间炔选择性半加氢活性的催化剂，既能充分利用催化剂的活性中心提高反应的活性，同时操作简单便捷，有利于降低催化剂的制备成本，对工业的应用存在重要意义和价值。
发明内容：
本发明的一个目的在于解决现有问题，提供一种催化剂。
本发明的另一个目的在于提供一种催化剂的制备方法。
本发明还有一个目的在于提供一种催化剂应用。
本发明采用以下的技术方案：
本发明第一方面提供一种用硫醇类配体修饰的催化剂，所述催化剂的通式为M-Pd 4S或M-Pd 4S/X；所述M为硫醇类配体，用于修饰Pd 4S；所述X为载体。
优选的，所述载体X选自C、CaCO 3、α-Al 2O 3、γ-Al 2O 3、氧化铈、分子筛、氧化硅、氧化钛和硅藻土中的至少一种。
优选的，所述硫醇类配体M选自直链硫醇和芳香族硫酚中的至少一种。
进一步优选的，所述直链硫醇选自正丁硫醇、巯基乙酸、正己硫醇、1-辛硫醇和十二硫醇中的至少一种；所述芳香族硫酚选自苯硫酚、3,4-二氟苯硫酚、1-氯苯硫酚、3,4-二甲基苯硫酚和4-叔丁基苯硫酚中的至少一种。
本发明第二方面提供一种用硫醇类配体修饰的催化剂的制备方法：包括以下步骤：
将Pd 4S或Pd 4S/X分散于极性有机溶剂中，通入含氢气的气体并保持气体氛围，加入硫醇类配体M，搅拌、抽滤、干燥，得到M-Pd 4S催化剂或M-Pd 4S/X催化剂。
优选的，所述极性有机溶剂选自DMF、乙腈和醇类溶剂中的至少一种。
优选的，所述含氢气的气体氛围由氢气和保护气体按体积比1:(0-4)组成，所述气体氛围的压力为0.5-5个大气压，进一步优选的，氢气和保护气体按体积比1:(0-1)组成，保护气体选自Ar和N 2中的一种。
优选的，所述硫醇类配体M:Pd的摩尔比为(0.02-1.1):1。
进一步优选的，所述硫醇类配体M:Pd的摩尔比为(0.1-0.8):1。
优选的，所述搅拌的时间为10min-12h。
优选的，所述搅拌的温度为50-120℃。
进一步优选的，所述搅拌的温度为60-100℃。
本发明第三方面还提供一种由上述催化剂或上述制备方法得到的催化剂的应用，应用于中间炔化合物半加氢。
优选的，所述中间炔化合物选自1-苯基-1丙炔、1-苯基-1-戊炔、二苯乙炔、4-苯基-3-丁炔-2-酮、4-辛炔、3-苯基-2-丙炔-1-醇和苯丙炔酸甲酯中的至少一种。
优选的，所述中间炔化合物与Pd的摩尔比为(1000-4000):1。
一种催化剂应用于中间炔化合物半加氢的方法，包括以下步骤：
将极性有机溶剂转移至反应瓶中，选取中间炔化合物为底物放至反应瓶中分散，设置温度为20-80℃，加入本发明催化剂，底物与Pd的摩尔比为(1000-4000):1，置换氢气，保持1-3个大气压的氢气压力，进行搅拌。
炔烃加氢一般分为两步加氢，第一步炔烃加氢反应生成烯烃，再进一步由烯烃深度加氢反应生成烷烃，本发明所述的炔烃半加氢是指第一步炔烃加氢生成烯烃的过程，故称之为炔烃半加氢。
化学修饰(chemical modification)是指用吸附、涂敷、聚合、化学反应等方法把活性基团或催化物质等附着在被修饰物表面。
对于本发明催化剂的制备Pd 4S可以选用纳米级材料，其形貌包括但不限于颗粒状、片状、棒状。
本发明采用的是对Pd 4S或Pd 4S/X进行修饰大位阻的配体，来实现炔烃的吸附与烯烃的脱附达到烯烃的高选择性。通入含氢气的气体并保持气体氛围，采用硫醇类配体M修饰Pd 4S或Pd 4S/X，制备得到M-Pd 4S催化剂或带有载体的M-Pd 4S/X催化剂，利用本发明催化剂实现在炔烃半加氢反应中对中间炔化合物具有高选择性。
有益效果：
(1)在含氢气的气体氛围下对Pd 4S或Pd 4S/X修饰硫醇类配体后，制备得到的催化剂对中间炔化合物半加氢具有较高的选择性，选择性可达到97％以上。
(2)本发明的催化剂对中间炔化合物半加氢反应的转化率较高，转化率可达到99％以上。
(3)本发明制备得到的催化剂稳定性高，多次套用未明显失活，套用8次，选择性仍可达到98％以上。
(4)制备本发明催化剂所使用修饰的硫醇类配体量少，价格低廉，重现性、稳定性好，降低成本，有利于工业应用。
(5)本发明催化剂的制备方法操作简单、工艺简便，具有普适性。
附图说明：
图1(a)为实施例1中Pd Ns以1-苯基-1-丙炔为底物进行半加氢反应的转化率及选择性曲线图；
图1(b)为实施例1中Pd 4S Ns以1-苯基-1-丙炔为底物进行半加氢反应的转化率及选择性曲线图；
图1(c)为实施例1中M-Pd 4S Ns催化剂以1-苯基-1-丙炔为底物进行半加氢反应的转化率及选择性曲线图(M为正丁硫醇)。
图2为实施例2中修饰正丁硫醇前后的红外图谱，(1)为修饰正丁硫醇后出现的正丁基的峰。
图3为实施例2中定时取样通过气相色谱进行产物的检测的色谱图。
图4为实施例3中M-Pd 4S/γ-Al 2O 3催化剂进行半加氢反应实验套用8次的循环稳定性实验结果图(M为正丁硫醇)。
图5为对比例1中Pd/γ-Al 2O 3用于半加氢实验的转化率和选择性曲线图。
图6为对比例1中Pd 4S/γ-Al 2O 3用于半加氢实验的转化率和选择性曲线图。
图7为对比例1中M-Pd 4S/γ-Al 2O 3催化剂用于半加氢实验的转化率和选择性曲线图(M为正丁硫醇)。
图8为对比例2中第一组实验中得到催化剂的XRD图。
图9为对比例2中第二组实验中得到催化剂的XRD图。
图10为对比例2中第一组实验制备的催化剂进行透射电镜表征的透射电镜 图。
具体实施例：
下面将结合本发明实施例中的附图，对本发明的技术方案进行描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1：二维钯纳米片制备催化剂进行半加氢反应
S1：将Pd 4S Ns分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到M-Pd 4S Ns催化剂备用(M为正丁硫醇)。
S2：将Pd摩尔质量相同的Pd Ns、Pd 4S Ns以及制备得到的M-Pd 4S Ns催化剂分别以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
图1为(a)Pd Ns、(b)Pd 4S Ns、(c)M-Pd 4S Ns催化剂对1-苯基-1-丙炔进行半加氢反应的转化率和选择性曲线图。
实施例2
S1：将Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。图2是修饰正丁硫醇前后的红外图谱，能够看出修饰正丁硫醇后在1400cm-1左右出现了明显的正丁基的峰，说明正丁硫醇修饰成功。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速 为1000rpm并打开搅拌。定时取样通过气相色谱进行产物的检测，图3为定时取样通过气相色谱进行产物的检测的色谱图，说明本发明催化剂用于半加氢反应的生成产物为烯烃。
实施例3：本发明催化剂套用的稳定性
S1：将Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为90℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
S3：继续将所制备得到的催化剂进行8次循环套用。图4为M-Pd 4S/γ-Al 2O 3催化剂进行半加氢反应实验套用8次的循环稳定性实验结果图，其转化率与选择性曲线如图4所示，能够看出本发明催化剂套用8次后选择性仍达到98％以上，稳定性良好。
实施例4
S1：将Pd 4S/X分散于DMF溶剂中，通入一个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/X催化剂备用(M为正丁硫醇)。
S2：将Pd摩尔质量相同的Pd/X和制备得到的M-Pd 4S/X催化剂分别以1-苯基-1-丙炔作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表1为不同载体制备催化剂进行半加氢反应的实验结果数据表，可以看出本发明制备方法用不同载体制备所得催化剂用于半加氢反应的选择性均在98％以上，均具有较高的选择性。
表1.不同载体制备催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000001
本实施例中，载体还可以是分子筛、氧化硅、氧化钛和硅藻土。
实施例5
S1：将Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入一个氢气大气压的氢气反应10min，保持气体氛围，加入不同硫醇类配体M，使得M:Pd的摩尔比为(0.02-1.1):1，搅拌的时间为10min-12h，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用。其中不同实验制备条件如下表2所示。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
不同硫醇类配体的种类、不同硫醇类配体用量以及不同搅拌的时间制备M-Pd 4S/γ-Al 2O 3催化剂用于半加氢反应的实验结果数据如下表2所示。能够看出：不同硫醇类配体都能够修饰Pd 4S，不同硫醇类配体位阻效应不同，对于不 同的底物可能效果不同，但是都能够很明显的提高对中间炔化合物半加氢的选择性。用于修饰的硫醇类配体的用量也有影响，当硫醇类配体M:Pd的摩尔比为(0.02-1.1):1时，炔烃转化>99％时烯烃的选择性较高，均达到98％以上，其中，硫醇类配体用量的最佳范围在(0.1-0.8):1之间。另外，搅拌的时间也有一定的影响，其中搅拌的时间为10min-12h时，炔烃转化>99％时烯烃的选择性均达到98％以上，为最佳范围。
表2.不同硫醇类配体的种类、不同硫醇类配体用量以及不同搅拌的时间制备M-Pd 4S/γ-Al 2O 3用于半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000002
Figure PCTCN2021071075-appb-000003
实施例6
S1：将Pd 4S/γ-Al 2O 3催化剂分散于DMF溶剂中，通入一个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为12h，搅拌的温度为50-120℃，抽滤出催化剂、用超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表3为不同搅拌的温度制备的M-Pd 4S/γ-Al 2O 3催化剂用于半加氢反应的实验结果数据，能够看得出当搅拌的温度为50-120℃时，炔烃转化>99％时烯烃的选择性均达到98％以上，当搅拌的温度小于60℃时，以及当搅拌的温度大于100℃时，炔烃转化>99％时烯烃的选择性有所降低，因此最适温度在60-100℃之间。
表3.不同搅拌的温度制备催化剂用于半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000004
实施例7
S1：取Pd摩尔质量相同的Pd 4S/γ-Al 2O 3分散于不同有机溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.3:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤、抽滤、干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表4为不同有机溶剂用于修饰硫醇类配体进行半加氢反应的实验结果数据，从数据可以分析出修饰过程的溶剂为DMF、乙腈、乙醇这些极性有机溶剂时，制备得的催化剂对烯烃选的择性更高，而使用正己烷这类非极性有机溶剂效果差很多，其中DMF作为溶剂的修饰效果最好。
表4.不同有机溶剂修饰硫醇类配体进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000005
Figure PCTCN2021071075-appb-000006
实施例8
S1：将Pd摩尔质量相同的Pd 4S/C分散于不同DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.5:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤、抽滤、干燥12h后制备得M-Pd 4S/C催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/C催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的醇类溶剂转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为20-80℃，加入相应量催化剂，底物与pd的摩尔比为(1000-4000):1，置换3次氢气后保持反应瓶中有1-3bar的氢气，设置转速为1000rpm并打开搅拌。表5为本发明催化剂进行半加氢反应的不同实验条件及结果数据。可以看出，本发明催化剂在不同条件下进行半加氢反应，炔烃转化>99％时烯烃的选择性均可达到98％以上。
表5.本发明催化剂进行半加氢反应的不同实验条件及结果数据
Figure PCTCN2021071075-appb-000007
实施例9
S1：将Pd摩尔质量相同的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为100℃，抽滤出催化剂，超纯水洗涤、抽滤、干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂选用不同的中间炔化合物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表6为M-Pd 4S/γ-Al 2O 3催化剂对于不同中间炔化合物的半加氢实验结果数据，炔烃转化>99％时烯烃的选择性可达到98％以上，能看出制备得到的M-Pd 4S/γ-Al 2O 3催化剂对于不同的中间炔化合物都具有很高的选择性。
表6.制备得到的M-Pd 4S/γ-Al 2O 3催化剂对于不同中间炔化合物的半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000008
实施例10
S1：将Pd摩尔质量相同的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤、抽滤、干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用 (M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂分别以不同烯烃和炔烃的混合物作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表7为本发明催化剂对烯烃和炔烃的混合物进行半加氢反应的实验结果数据，可见本发明催化剂对不同烯烃和炔烃的混合物有着优异的催化活性及选择性，相应烯烃的选择性能长时间维持在98％以上。
表7.本发明催化剂对烯烃和炔烃的混合物作为底物进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000009
实施例11
S1：将Pd摩尔质量相同的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入含氢气的气体反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.6:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂以1-苯基-1-丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速 为1000rpm并打开搅拌。
表8为氢气和保护气体体积比不同与气体氛围的压力不同制备本发明催化剂进行半加氢反应的实验结果数据，可以看出当气体氛围中氢气和保护气体按体积比1:(0-4)组成，制备本发明催化剂进行半加氢反应1-苯基-1-丙炔转化>99％时，烯烃的选择性可达到98％以上，其中，当氢气体积含量为100％时，选择性效果最好；另外，气体氛围的压力为0.5-5个大气压时，制备本发明催化剂进行半加氢反应1-苯基-1-丙炔转化>99％时，烯烃的选择性良好，可达到98％以上。表8.氢气和保护气体体积比不同与气体氛围的压力不同制备本发明催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000010
对比例1
S1：选取Pd质量分数为1％的Pd/γ-Al 2O 3分散于Na 2S的水溶液中，使得Pd:S的摩尔比为4:1，升温至150℃，保持氢气1Mpa的压力下，反应3h，冷却、抽滤、干燥，得到Pd 4S/γ-Al 2O 3。
S2：将制备好的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂， 超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S3：将Pd/γ-Al 2O 3和制备得到的Pd 4S/γ-Al 2O 3以及M-Pd 4S/γ-Al 2O 3催化剂分别进行以1-苯基-1-丙炔为底物的半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表9为Pd/γ-Al 2O 3、Pd 4S/γ-Al 2O 3、M-Pd 4S/γ-Al 2O 3催化剂进行半加氢反应实验结果数据，图5是Pd/γ-Al 2O 3用于半加氢实验的转化率和选择性曲线图，图6为Pd 4S/γ-Al 2O 3用于半加氢实验的转化率和选择性曲线图，图7为M-Pd 4S/γ-Al 2O 3催化剂用于半加氢实验的转化率和选择性，可以看出只有M-Pd 4S/γ-Al 2O 3催化剂对于中间炔化合物半加氢具有高选择性，其选择性不是来单纯来源于Pd 4S也不是正丁硫醇的修饰而是二者共同作用的结果。
表9.Pd/γ-Al 2O 3、Pd 4S/γ-Al 2O 3、M-Pd 4S/γ-Al 2O 3催化剂进行半加氢反应实验结果数据对比
Figure PCTCN2021071075-appb-000011
对比例2
第一组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将3,4二氟苯硫酚加入混合物中，然后加热至60℃，设置转速为1000rpm并打开搅拌，搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第二组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将3,4二氟苯硫酚加入混合物中加热至60℃，置换3次氢气后保持反应瓶中有1bar的氢气，设 置转速为1000rpm并打开搅拌搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第三组：将0.1gPd 4S/C分散于5mL DMF中的高压玻璃瓶中。将3,4二氟苯硫酚加入混合物中，然后加热至60℃，设置转速为1000rpm并打开搅拌，搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第四组：将0.1gPd 4S/C分散于5mL DMF中的高压玻璃瓶中。将3,4二氟苯硫酚加入混合物中加热至60℃，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
将所得的四组催化剂用于加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表10为四组制备的催化剂进行半加氢反应实验结果数据。能够看出修饰过程中不通入氢气制备的催化剂活性相差不大，但是选择性却差很多。图8为第一组实验中得到催化剂的XRD图，图9为第二组实验中得到催化剂的XRD图，图10为第一组实验制备的催化剂进行透射电镜表征的透射电镜图。通过图10透射电镜我们能看到第一组不通氢气制备得到的催化剂部分位置能够看到对应于Pd 4S晶相的晶格条纹间距为d＝0.228nm，但是其对应的XRD图中Pd 4S的特征峰基本上看不到，说明按照第一组反应条件(无氢气)得到的催化剂虽然出现了很少部分的Pd 4S产物，但是Pd 4S产率低下且没有很好的晶型结构，而第二组通入氢气制备得到的催化剂XRD图中Pd 4S特征峰明显。同样的，与第一组反应条件相比，第三组反应条件(Pd 4S在无氢气条件中)相较于第一组实验选择性没有明显提高，第四组反应条件下(Pd 4S在氢气条件中)得到的催化剂对中间炔半加氢具有高选择性。这是由于在氢气氛围下会生产得到稳定的Pd 4S晶相产物，并且在氢气条件下用硫醇类配体修饰得到硫醇类配体修饰的Pd 4S催化剂，其对于中间炔半加氢的选择性更高，烯烃的选择性能够达到99％以上，这在炔烃半氢化的领域是突破性的进展。而在修饰过程中不通入氢气所制备的催化剂虽能制备得到少量的Pd 4S，由于产物结晶度差，且没有进一步在氢气条件下修饰硫 醇类配体，但是与通氢气制备的催化剂相比较差很多。因此制备催化剂的过程通入氢气能使Pd 4S晶相稳定并且使配体更好地修饰上去，起到对烯烃高选择性的效果。
表10.不同条件下制备催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000012
对比例3
第一组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将正丁硫醇加入混合物中，然后加热至60℃，设置转速为1000rpm并打开搅拌，搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第二组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将巯基乙醇加入混合物中，然后加热至60℃，设置转速为1000rpm并打开搅拌，搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第三组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将正丁硫醇加入混合物中加热至60℃，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
第四组：将0.1gPd/C分散于5mL DMF中的高压玻璃瓶中。将巯基乙醇加入混合物中加热至60℃，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌搅拌12小时。用丙酮离心收集产物。将产物分散在乙醇中以备进一步使用。
将所得的四组催化剂用于半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。下表11为四组不同实验条件制备催化剂进行半加氢反应的实验结果数据。能够看出直链硫醇修饰Pd无论通氢气与否都无法制备用于中间炔半加氢反应的高选择性催化剂，原因在于直链硫醇的C-S键难以断裂，无法生成Pd 4S，因此直链硫醇无法修饰上去起到提高烯烃选择性的效果。
表11.不同实验条件制备催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000013
对比例4
S1：将Pd摩尔质量相同的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得M-Pd 4S/γ-Al 2O 3催化剂备用(M为正丁硫醇)。
S2：将制备得到的M-Pd 4S/γ-Al 2O 3催化剂分别以不同端炔化合物作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设 置转速为1000rpm并打开搅拌。表12为本发明催化剂以不同端炔化合物为底物进行半加氢反应的实验结果数据，可见本发明催化剂对端炔化合物的半加氢选择性低，均达不到80％，因此不适用于端炔化合物半加氢反应。
表12.本发明催化剂以不同端炔化合物为底物进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000014
对比例5
S1：将Pd质量分数为1％的Pd/γ-Al 2O 3分散于不同量的Na 2S水溶液中，升温至150℃，保持氢气1Mpa的压力下，反应3h，冷却、抽滤、干燥，得到PdxSy/γ-Al 2O 3。
S2：将Pd摩尔质量相同的PdxSy/γ-Al 2O 3分散于DMF溶剂中，通入一个氢气大气压的氢气反应10min，保持气体氛围，加入正丁硫醇作为硫醇类配体M，使得M:Pd的摩尔比为0.4:1，搅拌的时间为12h，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到催化剂A、催化剂B、催化剂C备用。
S3：将制备得到的催化剂A、催化剂B、催化剂C以1-苯基-1-丙炔作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表13为不同PdxSy的晶型制备本发明催化剂进行半加氢反应的实验结果数据，从中得到Pd 4S作为含硫量最低的PdS相其制备得到的催化剂活性是最高的，并且Pd 4S更容易接受硫醇配体，制备的催化剂对烯烃的选择性最高。
表13.不同PdxSy的晶型制备本发明催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000015
对比例6
S1：用含硫化合物一般处理钯：将含硫化合物处理Pd得到Pd和含硫化合物的反应物。
S2：还原反应：升温温度至150℃，将制备得到的反应物在1:1的H 2:N 2流(100mL/min)中还原1小时，随后在N 2流中冷却，制备得到还原后的钯催化剂。
S3：用含硫化合物对钯进行第二次处理：将还原得到的钯催化剂加入100mL的己烷和含硫化合物的溶液中，其中，通过本体Pd金属含量测量的含硫化合物与Pd的摩尔比为2.5:1，搅拌30min后，在旋转蒸发器上蒸发溶剂，制备得到催化剂备用。
S4：测试效果：将制备得到的催化剂以1-苯基-1丙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000：1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表14为不同含硫化合物处理钯制备催化剂进行半加氢的实验结果数据，可以看出利用该方法制备催化剂用于半加氢反应，其对炔烃半加氢具有选择性，但 选择性不高，均达不到80％，远不如本发明催化剂达到的效果，不适用于中间炔化合物选择性半加氢反应。
表14.不同含硫化合物处理钯制备催化剂进行半加氢的实验结果数据
Figure PCTCN2021071075-appb-000016
对比例7
S1：将制备好的Pd 4S/γ-Al 2O 3分散于DMF溶剂中，通入1个氢气大气压的氢气反应10min，保持气体氛围，加入硫脲作为配体，使得硫脲:Pd的摩尔比为0.4:1，搅拌的时间为60min，搅拌的温度为80℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得催化剂A备用。
S2：分别将Pd摩尔质量相同的Pd 4S/γ-Al 2O 3、制备得到的催化剂A分别进行以1-苯基-1-丙炔为底物的半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，设置温度为60℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表15为Pd 4S/γ-Al 2O 3、催化剂A进行半加氢反应实验结果数据。由表中数据可知，硫脲作为配体并不能提高对于烯烃的选择性。
表15.Pd 4S/γ-Al 2O 3、硫脲-Pd 4S/γ-Al 2O 3进行半加氢反应的实验结果数据
Figure PCTCN2021071075-appb-000017
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖 的范围内。

Claims (10)

  1. 一种用硫醇类配体修饰的催化剂，其特征在于，所述催化剂的通式为M-Pd 4S或M-Pd 4S/X；所述M为硫醇类配体，用于修饰Pd 4S；所述X为载体。
  2. 根据权利要求1所述的催化剂，其特征在于，所述硫醇类配体选自直链硫醇和芳香族硫酚中的至少一种。
  3. 根据权利要求2所述的催化剂，其特征在于，所述直链硫醇选自正丁硫醇、巯基乙酸、正己硫醇、1-辛硫醇和十二硫醇中的至少一种；所述芳香族硫酚选自苯硫酚、3,4-二氟苯硫酚、1-氯苯硫酚、3,4-二甲基苯硫酚和4-叔丁基苯硫酚中的至少一种。
  4. 一种用硫醇类配体修饰的催化剂的制备方法，其特征在于，包括以下步骤，
    将Pd 4S或Pd 4S/X分散于极性有机溶剂中，通入含氢气的气体并保持气体氛围，加入硫醇类配体M，搅拌、抽滤、干燥，得到M-Pd 4S催化剂或M-Pd 4S/X催化剂。
  5. 根据权利要求4所述的制备方法，其特征在于，所述极性有机溶剂选自DMF、乙腈和醇类溶剂中的至少一种。
  6. 根据权利要求4所述的制备方法，其特征在于，所述气体氛围由氢气和保护气体按体积比1:(0-4)组成，所述气体氛围的压力为0.5-5个大气压。
  7. 根据权利要求4所述的制备方法，其特征在于，所述硫醇类配体M:Pd的摩尔比为(0.02-1.1):1。
  8. 一种由权利要求1-3任一项所述的催化剂或由权利要求4-7任一项所述的制备方法所制得的催化剂的应用，其特征在于，应用于中间炔化合物半加氢。
  9. 根据权利要求8所述的应用，其特征在于，所述中间炔化合物选自1-苯基-1丙炔、1-苯基-1-戊炔、二苯乙炔、4-苯基-3-丁炔-2-酮、4-辛炔，3-苯基-2-丙炔-1-醇和苯丙炔酸甲酯中的至少一种。
  10. 根据权利要求8所述的应用，其特征在于，所述中间炔化合物与Pd的摩尔比为(1000-4000):1。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117000302A (zh) * 2023-06-29 2023-11-07 苏州大学 一种配体修饰的Ru基催化剂及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111774096B (zh) * 2020-07-14 2021-12-03 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用
CN115608361B (zh) * 2021-10-08 2024-04-23 厦门大学 一种用于还原胺化的催化剂及其制备方法和应用
CN115874199B (zh) * 2022-07-18 2024-06-04 天津大学 以d2o为氘源的官能化氘代烯烃类化合物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140242389A1 (en) * 2011-10-19 2014-08-28 Nexdot Process for the thickness growth of colloidal nanosheets and materials composed of said nanosheets
US20140287237A1 (en) * 2011-10-19 2014-09-25 Nexdot Method of increasing the thickness of colloidal nanosheets and materials consisting of said nanosheets
CN111774096A (zh) * 2020-07-14 2020-10-16 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003236386A (ja) * 2002-02-12 2003-08-26 Nagoya Industrial Science Research Inst 水素化触媒及びアルケン化合物の製造方法
US8563092B2 (en) * 2010-09-14 2013-10-22 Jawaharial Nehru Centre For Advanced Scientific Research Formation of palladium sulfide
RU2451010C1 (ru) * 2011-01-11 2012-05-20 Закрытое Акционерное Общество "Ива Фарм" Палладиево-медные катализаторы гомогенного селективного окисления тиольных групп, комбинация и композиция на их основе и способ терапевтического воздействия
US20140066291A1 (en) * 2011-02-01 2014-03-06 The Regents Of The University Of Colorado, A Body Corporate Materials and methods for improving selectivity in heterogeneous catalysts and products thereof
CN103008008B (zh) * 2011-09-22 2015-12-09 江苏圣奥化学科技有限公司 含硫钯/炭催化剂、其制备方法及对苯二胺类防老剂的制备方法
CN103406150B (zh) * 2013-07-29 2015-01-07 上海应用技术学院 一种高分子负载金属钯配合物催化剂及其制备方法和应用
CN103831118B (zh) * 2014-01-26 2015-11-25 浙江工业大学 一种合成炭载硫化钯催化剂和硫代芳胺的方法
CN104383963B (zh) * 2014-11-20 2017-01-04 沈阳化工大学 一种配体修饰负载型乙炔加氢Pd催化剂及其制备方法
CN107442136B (zh) * 2017-09-06 2020-03-27 厦门大学 一种钯纳米催化剂的表面修饰方法及催化应用
CN109012694B (zh) * 2018-08-09 2020-07-10 厦门大学 一种核壳结构钯铜催化剂及其制备方法与催化应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140242389A1 (en) * 2011-10-19 2014-08-28 Nexdot Process for the thickness growth of colloidal nanosheets and materials composed of said nanosheets
US20140287237A1 (en) * 2011-10-19 2014-09-25 Nexdot Method of increasing the thickness of colloidal nanosheets and materials consisting of said nanosheets
CN111774096A (zh) * 2020-07-14 2020-10-16 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YANG ZHIQIANG, KLABUNDE KENNETH J., SORENSEN CHRISTOPHER M.: "From Monodisperse Sulfurized Palladium Nanoparticles to Tiara Pd(II) Thiolate Clusters: Influence of Thiol Ligand on Thermal Treatment of a Palladium(II)−Amine System", THE JOURNAL OF PHYSICAL CHEMISTRY C, AMERICAN CHEMICAL SOCIETY, US, vol. 111, no. 49, 1 December 2007 (2007-12-01), US , pages 18143 - 18147, XP055887523, ISSN: 1932-7447, DOI: 10.1021/jp0765751 *
ZHAO XIAOJING, LINGYUN ZHOU, WUYONG ZHANG, CHENGYI HU, LEI DAI, LITING REN, BINGHUI WU, GANG FU, NANFENG ZHENG: "Thiol Treatment Creates Selective Palladium Catalysts for Semihydrogenation of Internal Alkynes", CHEM, CELL PRESS, US, vol. 4, no. 5, 10 May 2018 (2018-05-10), US , pages 1080 - 1091, XP055887522, ISSN: 2451-9294, DOI: 10.1016/j.chempr.2018.02.011 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117000302A (zh) * 2023-06-29 2023-11-07 苏州大学 一种配体修饰的Ru基催化剂及其制备方法和应用
CN117000302B (zh) * 2023-06-29 2024-03-15 苏州大学 一种配体修饰的Ru基催化剂及其制备方法和应用

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