CN113042100B - Ligand patch modulated supported gold nanoparticle catalytic material, preparation method and application - Google Patents

Ligand patch modulated supported gold nanoparticle catalytic material, preparation method and application Download PDF

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CN113042100B
CN113042100B CN202110309017.5A CN202110309017A CN113042100B CN 113042100 B CN113042100 B CN 113042100B CN 202110309017 A CN202110309017 A CN 202110309017A CN 113042100 B CN113042100 B CN 113042100B
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polyamine
ligand
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CN113042100A (en
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万德成
李晨辉
金明
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Tongji 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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

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Abstract

The invention relates to a ligand patch modulated gold nanoparticle-loaded catalytic material, and a preparation method and application thereof. Preparing polymer gel microspheres with specific surface of hundreds of square meters per gram, containing a large number of mesopores and having the size of about hundred micrometers in a conventional suspension polymerization mode in the presence of a pore-foaming agent; preparing mesoporous microspheres with a large amount of active chlorobenzyl on the surface by covalent bonding of divinylbenzene and 4-vinylbenzyl chloride; benzyl chloride is substituted with a branched polyethyleneimine (polyamine) having a molecular weight below 2000 daltons, thereby introducing a polyamine polymer patch on the surface of the nanosphere. Finally, cationic polyamine is utilized to adsorb anionic chloroauric acid radicals and is quickly reduced on site, and the supported gold nanoparticles which are several nanometers in size, uniform in size, excellent in catalytic action and easy to recover are obtained. The ligand distributed in the patch form can also inhibit the aging of the gold nanoparticles to a certain extent. The material can be used as a durable and easily-recycled catalytic material.

Description

Ligand patch modulated supported gold nanoparticle catalytic material, preparation method and application
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to preparation of a gold nano material by using cheap and easily-obtained mesoporous polymer loaded ligand patches and application of the gold nano material in catalytic reduction.
Background
Gold nanoparticles continue to be a popular research topic in multiple fields in nearly more than twenty years due to unique catalytic effect, light effect and photo-thermal effect. The size and the size uniformity are important parameters of the gold nanoparticles and are directly related to the physicochemical properties of the gold nanoparticles, so that the control of the size and the size uniformity becomes important control parameters. At present, gold nanoparticles or ultra-small-sized nano clusters (0.1-3nm) with tiny and uniform sizes are successfully prepared by taking high-generation dendrimers, carbon organic frameworks and metal organic frameworks as templates. Mesoporous silica with precise pore size and high uniformity has also been successfully used to modulate gold nanoclusters. However, these templates generally have many synthesis steps, are expensive, and are difficult to produce on a large scale. On the other hand, gold nanoparticles of uniform size also often require strong ligands as regulators and stabilizers, such as mercapto or polysulfide ligands, but such strong ligands often inhibit the catalytic ability of the gold nanoparticles. If the weak ligand modulation is adopted, the gold nanoparticles are often larger, the catalytic efficiency is reduced, and the stability is reduced.
Another challenge often faced with gold nanoparticles used as catalysts is recovery, which otherwise can cause environmental hazards and product quality degradation, for example, minimal residue of metal catalysts in certain pharmaceutical manufacturing can also significantly degrade drug quality. The loading method is often used for assisting the catalyst recovery, and the separation cost is low generally. The loading method is an out-of-phase process, and the quality of gold nanoparticles directly generated on a carrier is often not high; the multi-step loading law tends to increase costs. The direct production of high quality gold nanoparticles on a support is a problem that is being addressed. The preparation and loading of noble metal nanoparticles by inorganic carriers has been widely studied, and the main application background is oxidation catalysis. In contrast, less support materials have been reported for use in highly reducing environments.
Aging of metal nanocatalysis materials can significantly reduce catalytic efficiency, and aging is a phenomenon that occurs almost universally in nanocatalysts. Ostwald aging of noble metal nanoparticles reduces the specific surface mainly through migration and fusion of metal ions, metal atoms and even metal nanoclusters. Such migratory fusions often require ligand assistance. Aging is accelerated when the migrating species are more readily dissolved or dispersed on the support surface or in the dispersion medium. Thus, the ligand may help to reduce the rate of aging when present in a discontinuous patch.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to design a cheap route for preparing gold nanoparticles which are loaded by microspheres, have the size less than 5 nanometers and are uniform in size.
It is a second object of the invention to prepare the microspheroidal supported catalytic particles.
A third object of the present invention is to utilize the above materials as catalysts for reduction reactions.
In order to achieve the above purpose, the solution of the invention is as follows:
a preparation method of mesoporous polymer microsphere modulated gold nanoparticles comprises the following steps:
in the presence of a pore-forming agent, 4-vinylbenzyl chloride and a divinylbenzene crosslinking agent are used as oil phase monomers, and mesoporous polymer microspheres are prepared in an aqueous medium by a suspension polymerization method under the action of a free radical initiator; carrying out polyamine functionalization on the chlorobenzyl groups on the surfaces of the microsphere pores by using low-molecular-weight branched polyethyleneimine; loading an anionic gold precursor onto a polyamine and reducing by heating produces loaded gold nanoparticles in situ.
Preferably, the porogen is toluene, xylene or chlorobenzene.
Preferably, the volume of the porogen is 40-60% of the total volume of the oil phase.
Preferably, the molar ratio of the 4-vinylbenzyl chloride to the divinylbenzene is 0.8-1.5: 1.
Preferably, the feeding amount of the branched polyethyleneimine is 15-100% of the mass of the mesoporous microsphere.
Preferably, the molecular weight of the branched polyethyleneimine is 600-2000 daltons.
Preferably, the gold precursor is chloroauric acid or chloroaurate, the pH is 6-9 to facilitate electrostatic adsorption, and the feeding amount is Au: the molar ratio of N to gold is 1:16 to 1:40, namely, the number of nitrogen atoms is 16 to 40 times that of gold atoms.
Preferably, the gold precursor is reduced by heating immediately after being adsorbed by the supported polyamine at a temperature of 60 to 80 ℃.
The gold nanoparticles with small and uniform size can be obtained by the preparation method.
The catalytic material is used for catalytic reduction of various substrates and has stable performance.
Because the ligand is loaded on the surface of the carrier in a patch mode instead of continuously, the aging of the gold nanoparticles can be better inhibited, and the catalyst is more durable.
Drawings
FIG. 1 shows a mesoporous polymeric microsphere;
FIG. 2 is a nitrogen adsorption isotherm of porous microspheres before (a) and after (b) loading a branched polyamine;
FIG. 3 is a transmission electron micrograph of gold nanoparticles;
FIG. 4 is a transmission electron microscope particle size distribution statistical chart of gold nanoparticles.
The invention relates to preparation and application of a gold-loaded nanoparticle with the size of only a few nanometers regulated and controlled by a ligand patch. Preparing polymer gel microspheres with specific surface of hundreds of square meters per gram, containing a large number of mesopores and having the size of about hundred micrometers in a conventional suspension polymerization mode in the presence of a pore-foaming agent; preparing mesoporous microspheres with a large amount of active chlorobenzyl on the surface by covalent bonding of divinylbenzene and 4-vinylbenzyl chloride; benzyl chloride is substituted with a branched polyethyleneimine (polyamine) having a molecular weight below 2000 daltons, thereby introducing a polyamine polymer patch on the surface of the nanosphere. Finally, cationic polyamine is utilized to adsorb anionic chloroauric acid radicals and is quickly reduced on site, and the supported gold nanoparticles which are several nanometers in size, uniform in size, excellent in catalytic action and easy to recover are obtained. The method is characterized in that polyamine is embedded on the surface of a carrier in a patch form of a plurality of nanometers, and can adsorb gold ions and reduce the gold ions in situ to obtain small and uniform gold nanoparticles. The ligand distributed in the patch form can also inhibit the aging of the gold nanoparticles to a certain extent. The material can be used as a durable and easily-recycled catalytic material.
The present invention will be further described with reference to the following examples.
Example 1 (Synthesis of mesoporous microspheres)
The mesoporous polymer is synthesized by adopting a suspension polymerization method in the presence of a pore-foaming agent. Polyvinyl alcohol 1788(1g) was dissolved well in deionized water (200mL), to which was added sodium chloride (4g), methylene blue solution (0.1 wt.%, 4mL), the resulting solution being the aqueous phase of the suspension. 4-vinylbenzyl chloride (13g,0.085mol), divinylbenzene (11g,0.085mol), azobisisobutyronitrile (AIBN, 0.1g) and a porogen toluene (24ml) were mixed as an oil phase. The oil phase was added dropwise to the aqueous phase with mechanical stirring at 350rpm and heated under nitrogen at 70 ℃ for 3 hours followed by 80 ℃ for 2 hours. Filtering to separate out particles, extracting with acetone for 24 hr, washing with dilute hydrochloric acid (pH 5-6) for 3 times, soaking in ethanol for 2 times, and vacuum drying at 50 deg.C to obtain bead-shaped particles.
The diameter of the sphere is within 100-2G, average pore diameter 3.4 nm (FIG. 2 a). The carrier material with very high specific surface area can be directly obtained on a large scale.
The present embodiment can obtain gold-loaded nanoparticles below 5nm, and such small-sized gold nanoparticles with high specific surface area generally have high catalytic efficiency.
Example 2 (polyamine functionalization of mesoporous microspheres and gold Nanowoad)
Branched polyethyleneimine (polyamine) (0.4g, molecular weight 2000Dalton,9.3mmol amino) was dissolved in ethanol (20ml), and the mesoporous microspheres (2g) of example 1 were added thereto and stirred at 80 ℃ for 6 h. Separating out the microspheres, soaking and washing the microspheres with ethanol, and drying the microspheres in vacuum. Elemental analysis determined the nitrogen content to be 2.6% and derived therefrom the loading of amino groups on the microspheres to be 1.86mmol NH/g. The specific surface area is reduced to 244m by the determination of a BET method2(FIG. 2b), indicating that a portion of the pores are blocked by the polyamine. According to theoretical calculations, polyamines having a molecular weight of 2000 daltons have a diameter of 1.86nm when they are present in the form of ideal spheres. The coverage of the polyamine on the surface of the carrier is 26.7%, and the surface coverage is not so high even if the polyamine is deformed into a cake shape. I.e. the polyamine ligands are distributed in patches on the surface of the support.
Polyamine microspheres (1g,1.86mmol NH/g) were dispersed in deionized water (7ml), and a solution of HAuCl4 (3ml,20mM, N: Au ═ 32:1 (mol: mol)) was added thereto, and the mixture was stirred vigorously at room temperature for 1min, followed by immediate heating at 80 ℃ for 30 min. The microspheres are separated by suction filtration, washed by distilled water and ethanol in sequence and dried in vacuum at 50 ℃.
BET method test shows that the specific surface area is from 244m after the polyamine is functionalized2The/g is reduced to 165m2The average mesopore size is increased to 4.8 nm, which indicates that the smaller mesopore part is blocked by the gold nanoparticles. The microspheres are ground and dispersed in ethanol for carbon film sample preparation, and transmission electron microscope analysis shows that the size of the gold nanoparticles is 3.9 +/-0.6 nm (figure 3), and the size distribution of the gold nanoparticles is relatively uniform with the standard deviation of 15 percent (as shown in figure 4).
Example 3 (catalytic reduction of Supported gold nanoparticles)
To an aqueous solution (20mL) containing 4-nitrophenol (0.06mM) and sodium borohydride (0.5g) was charged the supported catalyst of example 2 (0.1g), and stirred. The solution changed from red to colorless in half an hour, indicating that the 4-nitrophenol had been sufficiently reduced. The microspheres are filtered and separated, and are repeatedly used for catalytic reduction, and the red substrate can still be reduced into a colorless product within half an hour. No decrease in catalytic ability was observed in 6 repetitions, and the seventh time started to decrease. Its catalytic running frequency TOF is 197.1h-1Gold nanoparticles larger than size (TOF 0.72 h)-1See document j. mater. chem.a,2015,3,13519) high. The residual gold in the reducing solution was 1.27ppb (ppb: parts per billion) as measured by the induction plasma method. This result indicates very little gold loss. Since gold is difficult to exist as ions in a strongly reducing environment, the lost gold should exist in an atomic state.
Example 4 comparison of Patch-like distribution with continuous distribution of ligand
A supported gold nanoparticle catalyst (synthesized by a specific reference; j. mater. chem. a,2015,3,13519) was similarly prepared with a support having a continuous distribution of ligand polyamine instead of the catalyst of example 2, and the synthesized gold nanoparticle catalyst was 4.0 ± 1.5nm in size, which was very close to the catalyst of example 2. The same catalytic reduction experiment was carried out while keeping the same amount of gold atoms, and as a result, it was found that the new catalyst was low in efficiency and gradually decreased in the 4 th reuse. The main difference between the two catalysts is a patchy distribution of ligands, one continuous distribution. The comparison shows that the ligand distribution in patch can inhibit the catalyst aging to some extent. The reason may be that the patch does not facilitate gold atom migration, thereby inhibiting the aging rate to some extent.

Claims (2)

1. A preparation method of a ligand patch modulated supported gold nanoparticle catalytic material is characterized by comprising the following steps: in the presence of a pore-forming agent, 4-vinylbenzyl chloride and a divinylbenzene crosslinking agent are used as oil phase monomers, and mesoporous polymer microspheres are prepared in an aqueous medium by a suspension polymerization method under the action of a free radical initiator; carrying out polyamine functionalization on the chlorobenzyl groups on the surfaces of the microsphere pores by using low-molecular-weight branched polyethyleneimine; loading an anionic gold precursor onto a polyamine and heating to reduce to generate in situ loaded gold nanoparticles;
the pore-foaming agent is toluene, dimethylbenzene or chlorobenzene, and the volume of the pore-foaming agent is 40-60% of the total volume of the oil phase;
the molar ratio of the 4-vinylbenzyl chloride to the divinylbenzene is 0.8-1.5: 1;
the feeding amount of the branched polyethyleneimine is 15-100% of the mass of the mesoporous microsphere, and the molecular weight of the branched polyethyleneimine is 600-2000 daltons;
the gold precursor adopts chloroauric acid or chloroaurate; the pH value of the gold precursor is 6 to 9 when the gold precursor is loaded so as to facilitate electrostatic adsorption, and the feeding amount is Au: n = 1:16 to 1:40 molar ratio;
the gold precursor is immediately heated and reduced after being adsorbed by the loaded polyamine, and the temperature is 60-80 ℃.
2. The preparation method of claim 1 is used for obtaining a ligand patch modulated supported gold nanoparticle catalytic material.
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