CN108927216B - Patch-constrained porous carrier catalytic material and preparation method and application thereof - Google Patents
Patch-constrained porous carrier catalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a patch-constrained porous carrier catalytic material and a preparation method and application thereof, wherein the catalytic material comprises a porous carrier and nano composite particles loaded on the porous carrier, and the nano composite particles are patches containing precious metal nano particles; when in preparation, the nano composite particles are loaded on the surface of the porous carrier by adopting a concentrated emulsion polymerization method; the catalytic material is used as heterogeneous catalyst for the catalytic chemical reaction in water phase or oil phase reaction system. Compared with the prior art, the method has the advantages that the noble metal nanoparticles with the catalytic effect are restrained by the patches formed by the tree-shaped amphiphilic bodies and loaded on the surface of the porous carrier material, and the stability and the catalytic activity of the noble metal nanoparticles are regulated and controlled by utilizing the synergistic effect of the strong and weak ligands, so that the catalytic material is more durable, and the stability of the noble metal nanoparticles is good.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and relates to a patch-constrained porous carrier catalytic material, and a preparation method and application thereof.
Background
Currently, about 60% of chemical products require catalytic materials in production, and heavy metal catalysts are important catalytic materials. The heavy metal catalyst is expensive, and more importantly, leakage of the heavy metal catalyst can cause serious environmental pollution, and metal residues in the product can also seriously affect the product quality, especially the production of medicaments for human bodies, so that the stability and the recoverability of the heavy metal catalyst are very important in some catalytic processes, and the key is the design of a ligand and a carrier of the noble metal.
The leakage of the zero-valent noble metal nanoparticles is mainly realized in the following ways: firstly, the loss is caused after the atomic state is dissolved in the medium; and the second is loss in an ionic state. In addition, the noble metal nanoparticles may also cause a decrease in catalytic efficiency due to aging (the particles become larger and the catalytic surface area becomes correspondingly smaller). The aging of the noble metal nanoparticles is determined by the metal ligands and the carrier morphology, and the leakage is related to the oxidative properties of the environment and the coordination of the medium molecules besides the metal ligands. When the micromolecule mercaptan is used as the ligand, the action of the micromolecule mercaptan and the noble metal is strong, the noble metal is not easy to lose and age, but the mercaptan ligand easily enables the noble metal to lose the catalytic activity; while weak ligands (such as amines and alcohols) have weak action with noble metals, which ensures high catalytic activity of noble metals, but easily causes loss and aging of noble metal nanoparticles.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a patch-constrained porous carrier catalytic material, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a patch-constrained porous support catalytic material comprises a porous support and nanocomposite particles loaded on the porous support, wherein the nanocomposite particles are patches containing precious metal nanoparticles.
Further, the patch is a tree-like amphiphile.
Further, the dendriform amphiphilic parent is a sulfydryl modified polyethyleneimine dendriform amphiphilic parent.
As a preferred technical scheme, the polyethyleneimine is hyperbranched Polyethyleneimine (PEI).
Further, in the tree-like amphiphilic substance, 0.2-2% of the ethylene imine repeating units are sulfhydrylated.
Further, 5-60% of the ethyleneimine repeating units in the dendrimer amphiphile are alkylated with polystyrene.
As a preferred technical scheme, the polystyrene is glycerol ether terminated polystyrene.
As a preferred technical scheme, the molecular weight of the polystyrene is 1000-30000 daltons.
A preparation method of a patch-constrained porous carrier catalytic material is characterized in that a concentrated emulsion polymerization method is adopted to load nano composite particles on the surface of a porous carrier.
Further, the method comprises the following steps: the catalytic material is prepared by mixing the oil phase, the water phase and the stabilizer and then carrying out free radical polymerization reaction by taking the nano composite particles and the surfactant as the stabilizer, taking the styrene monomer, the divinyl benzene and the free radical initiator as the oil phase and taking the buffer aqueous solution as the water phase.
As a preferable technical scheme, the mass ratio of the nano composite particles to the surfactant is 0.6-2: 1. After the concentrated emulsion is solidified into a porous material, the surfactant on the surface is removed by soxhlet extraction or soaking with ethanol.
Further, the surfactant is a nonionic small molecular surfactant, the radical initiator is azobisisobutyronitrile, and the pH value of the buffer aqueous solution is 4-8.
As a preferable technical scheme, the nonionic small molecule surfactant is commercially available span 80.
Furthermore, the oil phase also contains toluene. The porogen toluene, as an optional component, can increase the surface area of the porous material.
As a preferred technical scheme, the volume ratio of the styrene monomer, the divinyl benzene and the toluene is 40-80:20-60: 0-30.
Specifically, the preparation method of the patch-constrained porous carrier catalytic material comprises the following steps:
(1) preparation of oil-dispersible dendrimer-stabilized noble metal nanocomposite particles:
dispersing noble metal (gold, silver, platinum and palladium) nanoparticles stabilized by thiolated polyethyleneimine (0.2-2% of repeat units in polyethyleneimine are thiolated) obtained in any mode into chloroform, and carrying out oleophylic alkylation by using glycerol ether terminated polystyrene to ensure that 5-60% of ethylene imine repeat units in polyethyleneimine are alkylated by the glycerol ether terminated polystyrene to obtain nano composite particles;
(2) expressing the nano composite particles on the pore surface of the porous material in a patch-constrained manner
Mixing the oil-dispersible precious metal nano composite particles and a nonionic small molecular surfactant as a common stabilizer, mixing a styrene monomer, divinylbenzene (and optional toluene) and a proper amount of a free radical initiator (such as azobisisobutyronitrile) to form an oil phase, taking a buffer aqueous solution with the pH value of 4.0-8.0 as a water phase, and dropwise adding the water phase to the oil phase under strong stirring to form a water-in-oil concentrated emulsion, wherein the volume of the water phase accounts for more than 75% of the total volume of the system; after the water is dripped, the mixture is continuously stirred for a certain time, and the obtained pasty concentrated emulsion is transferred into a beaker or other containers with big mouth and small bottom to be heated for free radical polymerization; and after the emulsion is fully solidified, taking out the lump material, and washing with ethanol or performing Soxhlet extraction to remove the small molecular surfactant to obtain the porous carrier catalytic material.
The application of a patch-constrained porous carrier catalytic material as a heterogeneous catalyst for catalyzing the performance of chemical reactions in aqueous or oil phase reaction systems.
As a preferable technical scheme, the catalytic material is used for reductive catalytic reaction, solid massive catalytic material is put into a reaction system, and the catalytic massive material is directly fished out or filtered out after the reaction is finished and is reserved for next use.
Directly putting the porous carrier catalytic material (which can be crushed into small blocks) into a water phase or oil phase reaction system for heterogeneous catalytic reaction, filtering and collecting the material after the reaction operation is finished or directly fishing out the catalytic material for reutilization. The catalytic monolith may be stored in a reducing environment (e.g., aqueous sodium borohydride solution) at ordinary times.
In the porous carrier catalytic material, sulfydryl modified (containing 0.2-2% of thiol functional groups) polyethyleneimine tree-like amphiphilic bodies are used as metal multi-ligands (thiol and amino are respectively used as strong and weak ligands) to replace the conventional single ligand and noble metal nano-particle action, noble metal ion reduction is regulated and controlled in water to obtain nano composite particles, and weak ligands in the multi-ligands can still play a good stabilizing role. The surface of the nano composite particle is only partially occupied by mercaptan, and high catalytic activity can still be maintained. The generation of the nano noble metal nano particles can be regulated and controlled by introducing a trace amount of thiol functional groups (sulfydryl) on the rigid dendritic ligand, and good catalytic activity is reserved.
In the porous carrier catalytic material, the functional tree-shaped amphiphilic substance is self-assembled at the interface of the prepared concentrated emulsion to form patch-shaped discrete micro-areas, and the ligands in the patches are dense while the non-ligand inert environment is outside the patches. The patch is formed because the functionalized tree-like amphiphiles (nano-scale) or the aggregates (micron-scale) thereof are dispersed in the small molecule surfactant, and when the functionalized tree-like amphiphiles and the small molecule surfactant are assembled together at the interface to form a film-like structure, the functionalized tree-like dispersoids form an island-like structure in the film. This structure provides a special microenvironment, so that the surface is no longer of a uniform structure. The noble metal nanoparticles may be constrained by patches on the porous support, and thus be more stable and durable. Taking polyethyleneimine with a very small amount of thiol groups as a metal ligand, regulating and synthesizing noble metal nanoparticles in a water phase, then driving the noble metal nanoparticles into a chloroform phase by a salting-out method, purifying by ultracentrifugation, and then partially alkylating amino groups of the polyethyleneimine by glycerol ether-terminated polystyrene to obtain amphiphilic nano composite particles; the nano composite particles and the micromolecular surfactant are used for jointly stabilizing the water-in-oil type concentrated emulsion under the condition that the pH value is 4-8; polymerizing and curing the concentrated emulsion to form a through hole framework, washing off the micromolecular surfactant to obtain the porous block material, wherein the surface of the block material is expressed by a discrete patch internally restricted with the noble metal nano particles. The restraining effect of the patch can delay the aging of the noble nano-metal particles, so that the catalytic material is more durable.
Compared with the prior art, the invention has the following characteristics:
1) according to the invention, noble metal nanoparticles with a catalytic effect are restrained by patches formed by tree-shaped amphiphilic bodies and loaded on the surface of a porous carrier material, and the stability and catalytic activity of the noble metal nanoparticles are regulated and controlled by utilizing the synergistic effect of strong and weak ligands, so that the catalytic material is more durable; meanwhile, metal species are constrained in a ligand patch environment, and a non-ligand inert matrix is arranged outside the patch, so that metal atom loss and direct fusion of metal nanoparticles can be inhibited, and the stability of the noble metal nanoparticles is facilitated;
2) the size of the noble metal nano particles is controlled by utilizing the sulfur-containing tree-shaped amphiphiles, so that the noble metal nano particles have smaller size and higher stability, the durability of the noble metal nano particles is improved, and the noble metal nano particles are easy to separate, recover and reuse;
3) the molecular weight of the dendritic amphiphilic substance is large, the effect between the dendritic amphiphilic substance and the carrier is stronger, and the dendritic amphiphilic substance is difficult to fall off from the carrier, so that the prepared catalytic material is very suitable for being used in an aqueous medium;
4) the noble metal nano particles are restrained on the carrier by the patch, and the inert non-metal ligands are arranged around the patch, so that the aging migration of metal atoms or metal nano particles is more difficult, the stability is higher, and the metal loss can be reduced to a certain extent and the product quality can be improved.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of the porous support catalytic material prepared in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
dissolving hyperbranched polyethyleneimine (PEI, 0.43g and 10mmol of amino hydrogen) in methanol (5m L), introducing nitrogen for deoxidation for 10 minutes, sequentially adding trifluoroacetic acid (0.057g and 0.5mmol) and ethylene sulfide (0.00625g and 0.1mmol), sealing under nitrogen, and stirring overnight to obtain the sulfhydryl modified PEI.
Adding water solution (83m L) containing chloroauric acid (0.83mmol), heating to 85 deg.C with nitrogen, rapidly adding the above sulfhydryl modified PEI with a syringe under stirring, reacting at 85 deg.C for 6-12 hr to obtain mauve to black solution, adjusting pH to 12, adding sodium chloride until saturation, and extracting colored part with chloroform.
Mixing the chloroform solution and glycerol ether terminated polystyrene (PS, 6.75g, molecular weight 4500, 0.15mmol, synthesis method see document Wan DC, Yuan JJ, Pu HT. macromolecules 2009,42,1533) to form a solution, and reacting at room temperature for 6 days; and precipitating with methanol, collecting the precipitate, and drying to obtain the nano composite particle Au-PEI @ PS.
Example 2:
the same procedure as in example 1 was repeated except that the chloroauric acid in example 1 was replaced with an equimolar amount of silver nitrate to prepare nanocomposite particles Ag-PEI @ PS.
Example 3:
nanocomposite particles Pt-PEI @ PS were prepared in the same manner as in example 1 except that the chloroauric acid in example 1 was replaced with an equimolar amount of potassium chloroplatinate, and the reduction reaction of potassium chloroplatinate was performed at room temperature using an aqueous solution of sodium borohydride (12 equivalents of platinum ion) as a reducing agent.
Example 4:
the platinum nanoplatelets of example 3 were expressed on the pore surface of the porous material by a dense emulsion polymerization method as follows:
the oil phase of the concentrated emulsion is composed of styrene (St), divinyl benzene (DVB), toluene and Azodiisobutyronitrile (AIBN) initiators, wherein St: DVB is 8:2 (volume ratio), St + DVB: toluene is 7:3 (volume ratio), and the mass of AIBN is 1% of that of the oil phase; Pt-PEI @ PS and span 80 are used as emulsion stabilizers, the dosage of the emulsion stabilizers is 10% of the mass of the oil phase, and the Pt-PEI @ PS: span 80 is 6:4 (mass ratio). The aqueous phase consisted of a buffer solution at pH 6.86, the volume of which corresponded to 8 times the volume of the oil phase. Dropwise adding the water phase into the oil phase under strong stirring, continuously stirring for about 15 minutes after dropwise adding, and standing the formed emulsion in a convection heater at 70 ℃ for 12-24 hours; and taking out the solidified lump material, and extracting and washing the lump material by using ethanol for 10 hours to obtain a light brown rigid solid, namely the porous carrier catalytic material loaded with the platinum nano particles. After the solid is crushed, the solid is dispersed in ethanol for transmission electron microscope observation (as shown in figure 1), and the noble metal nano particles are seen to be in discrete black dots.
The patch is arranged on the surface of the porous carrier, and the noble metal nano-beams are restricted in the patch, so that the non-ligand inert matrix is arranged outside the patch, the migration of metal atoms is difficult, the aging is inhibited, the service life of the catalyst is prolonged, and the metal residue in the product and the medium is obviously reduced.
Example 5:
the Pt-PEI @ PS in example 4 is replaced by Au-PEI @ PS, and similar operation is carried out to prepare the porous carrier catalytic material loaded with the gold nanoparticles.
Example 6:
the catalytic properties of the porous support catalytic material loaded with gold nanoparticles of example 5 were determined as follows:
reacting NaBH4(0.2M L, 0.3M) and4-Nitrophenol (5m L, 1.1 × 10)-4M) mixing, immediately turning the system into red-yellow, and introducing nitrogen to remove oxygen; the porous carrier catalytic material (0.1g) loaded with gold nanoparticles was put into the reactor, gently stirred, and uv-vis light scanning was performed every several minutes, after about 55min, the spectrum at 400nm nearly disappeared, indicating that 4-nitrophenol had been substantially reduced. Taking out the massive catalytic material and putting the massive catalytic material into the next reaction. After 20 cycles, the catalytic reaction can still be completed within 55 min.
Example 7:
the porous carrier catalytic material loaded with gold nanoparticles in example 6 was replaced with the porous carrier catalytic material loaded with platinum nanoparticles, and similar operations were performed, and the catalytic reaction could be completed within 50 min.
Example 8:
the method comprises the steps of directly reacting polyethyleneimine with glycerol ether-terminated polystyrene to obtain PEI @ PS, and replacing span 80 in example 4 with the PEI @ PS with the same mass to similarly prepare the platinum nanoparticle-loaded porous carrier catalytic material. The porous material is characterized in that the inert matrix left after the span 80 is washed away is not filled around the final platinum nanobeam patch, but is filled with PEI @ PS.
0.1g of the porous carrier catalytic material (Pt-1) loaded with the platinum nanoparticles obtained in example 4 and the prepared porous carrier catalytic material (Pt-2) loaded with the platinum nanoparticles are respectively soaked in 100m L water, a solid is taken out after 30 days, a water sample is filtered, the content of metal platinum in the water is measured by induction plasma spectroscopy (ICP), the content of the platinum in the water is found to be about 130ppb, the platinum content is the same within an error range by repeating the steps for a plurality of times, which indicates that the platinum leakage reaches saturation, and the soaked catalytic material is used for catalytic reduction of 4-nitrophenol, so that the catalytic activity of the Pt-1 is always higher than that of the Pt-2, which indicates that the Pt-2 is aged more quickly.
Example 9:
a patch-constrained porous support catalytic material comprises a porous support and nanocomposite particles loaded on the porous support, wherein the nanocomposite particles are patches containing precious metal nanoparticles.
Wherein the patch is a tree-like amphiphile; the dendriform amphiphilic substance is sulfhydryl modified polyethyleneimine dendriform amphiphilic substance; in the tree-like amphiphile, 0.2% of ethyleneimine repeating units are sulfhydrylated; in the dendrimeric amphiphile, 5% of the ethyleneimine repeating units are alkylated by polystyrene.
When the catalytic material is prepared, the nano composite particles are loaded on the surface of the porous carrier by adopting a concentrated emulsion polymerization method. The specific method comprises the following steps: the catalytic material is prepared by mixing the oil phase, the water phase and the stabilizer and then carrying out free radical polymerization reaction by taking the nano composite particles and the surfactant as the stabilizer, taking the styrene monomer, the divinyl benzene and the free radical initiator as the oil phase and taking the buffer aqueous solution as the water phase.
Wherein the surfactant is a nonionic micromolecular surfactant, the free radical initiator is azobisisobutyronitrile, and the pH value of the buffer aqueous solution is 4; the oil phase also contained toluene.
The catalytic material is used as a heterogeneous catalyst for catalyzing chemical reaction in a water phase reaction system.
Example 10:
a patch-constrained porous support catalytic material comprises a porous support and nanocomposite particles loaded on the porous support, wherein the nanocomposite particles are patches containing precious metal nanoparticles.
Wherein the patch is a tree-like amphiphile; the dendriform amphiphilic substance is sulfhydryl modified polyethyleneimine dendriform amphiphilic substance; in the tree-like amphiphile, 2% of the ethyleneimine repeating units are sulfhydrylated; in the dendrimeric amphiphile, 60% of the ethyleneimine repeating units are alkylated with polystyrene.
When the catalytic material is prepared, the nano composite particles are loaded on the surface of the porous carrier by adopting a concentrated emulsion polymerization method. The specific method comprises the following steps: the catalytic material is prepared by mixing the oil phase, the water phase and the stabilizer and then carrying out free radical polymerization reaction by taking the nano composite particles and the surfactant as the stabilizer, taking the styrene monomer, the divinyl benzene and the free radical initiator as the oil phase and taking the buffer aqueous solution as the water phase.
Wherein the surfactant is a nonionic micromolecular surfactant, the free radical initiator is azobisisobutyronitrile, and the pH value of the buffer aqueous solution is 8; the oil phase also contained toluene.
The catalytic material is used as a heterogeneous catalyst for carrying out catalytic chemical reaction in an oil phase reaction system.
Example 11:
a patch-constrained porous support catalytic material comprises a porous support and nanocomposite particles loaded on the porous support, wherein the nanocomposite particles are patches containing precious metal nanoparticles.
Wherein the patch is a tree-like amphiphile; the dendriform amphiphilic substance is sulfhydryl modified polyethyleneimine dendriform amphiphilic substance; in the tree-like amphiphile, 1% of the ethyleneimine repeating units are sulfhydrylated; in the dendrimeric amphiphile, 35% of the ethyleneimine repeating units are alkylated by polystyrene.
When the catalytic material is prepared, the nano composite particles are loaded on the surface of the porous carrier by adopting a concentrated emulsion polymerization method. The specific method comprises the following steps: the catalytic material is prepared by mixing the oil phase, the water phase and the stabilizer and then carrying out free radical polymerization reaction by taking the nano composite particles and the surfactant as the stabilizer, taking the styrene monomer, the divinyl benzene and the free radical initiator as the oil phase and taking the buffer aqueous solution as the water phase.
Wherein the surfactant is a nonionic micromolecular surfactant, the free radical initiator is azobisisobutyronitrile, and the pH value of the buffer aqueous solution is 6; the oil phase also contained toluene.
The catalytic material is used as a heterogeneous catalyst for catalyzing chemical reaction in a water phase reaction system.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A patch-constrained porous carrier catalytic material is characterized by comprising a porous carrier and nano composite particles loaded on the porous carrier, wherein the nano composite particles are patches containing noble metal nano particles, the patches are tree-like amphiphilic bodies, and the tree-like amphiphilic bodies are sulfydryl modified polyethyleneimine tree-like amphiphilic bodies;
the preparation method of the catalytic material comprises the following steps:
sulfydryl modified polyethyleneimine dendriform amphiphilic substance is used as a metal multi-ligand, noble metal ion reduction is regulated and controlled in water to obtain nano composite particles, and 0.2-2% of ethyleneimine repeating units in the dendriform amphiphilic substance are sulfhydrylated before noble metal ions are reduced;
the nano composite particles and a surfactant are used as a stabilizer, and the nano composite particles are loaded on the surface of a porous carrier formed in the process of thick emulsion polymerization by adopting a thick emulsion polymerization method.
2. A patch-constrained porous support catalytic material as claimed in claim 1 wherein 5-60% of the ethyleneimine repeat units in the dendrimer amphiphile are alkylated with polystyrene.
3. A method for preparing a patch-constrained porous carrier catalytic material as claimed in any one of claims 1-2, wherein thiol-modified polyethyleneimine dendritic amphiphiles are used as metal multi-ligands, noble metal ions are controlled in water to reduce to obtain nanocomposite particles, and 0.2-2% of ethyleneimine repeating units in the dendritic amphiphilic amphiphiles are thiolated before the noble metal ions are reduced;
the nano composite particles and a surfactant are used as a stabilizer, and the nano composite particles are loaded on the surface of a porous carrier formed in the process of thick emulsion polymerization by adopting a thick emulsion polymerization method.
4. A method of preparing a patch-constrained porous carrier catalytic material as claimed in claim 3, wherein the method comprises: the catalytic material is prepared by mixing the oil phase, the water phase and the stabilizer and then carrying out free radical polymerization reaction by taking the nano composite particles and the surfactant as the stabilizer, taking the styrene monomer, the divinyl benzene and the free radical initiator as the oil phase and taking the buffer aqueous solution as the water phase.
5. The method as claimed in claim 4, wherein the surfactant is a non-ionic small molecule surfactant, the radical initiator is azobisisobutyronitrile, and the pH of the buffered aqueous solution is 4-8.
6. The method of claim 4 wherein the oil phase further comprises toluene.
7. Use of a patch-constrained porous carrier catalytic material as claimed in any one of claims 1 to 2 as a heterogeneous catalyst for catalysing a chemical reaction in an aqueous or oil phase reaction system.
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