CN113070100A - Trace thioether-assisted polyamine patch modulated load gold nanocluster and catalytic application thereof - Google Patents
Trace thioether-assisted polyamine patch modulated load gold nanocluster and catalytic application thereof Download PDFInfo
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- CN113070100A CN113070100A CN202110309232.5A CN202110309232A CN113070100A CN 113070100 A CN113070100 A CN 113070100A CN 202110309232 A CN202110309232 A CN 202110309232A CN 113070100 A CN113070100 A CN 113070100A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 57
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- 150000003568 thioethers Chemical class 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 title abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
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- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
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- 238000002360 preparation method Methods 0.000 claims description 11
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- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 5
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- 230000000694 effects Effects 0.000 abstract description 3
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- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DNOUKPGPAUUCPC-UHFFFAOYSA-N 2-methylsulfanylpropanal Chemical compound CSC(C)C=O DNOUKPGPAUUCPC-UHFFFAOYSA-N 0.000 description 1
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 description 1
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- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
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- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
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- 239000011943 nanocatalyst Substances 0.000 description 1
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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
- B01J31/02—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
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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
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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
- B01J35/60—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
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Abstract
The invention relates to a trace thioether-assisted polyamine patch modulated load gold nanocluster and catalytic application thereof. The invention can be prepared by only adopting polybutylece and weak multi-ligand, and the activity of the gold nanocluster is higher than that of a strong ligand counterpart. Firstly, covalently modifying and supporting polyamine on the surface of a mesoporous polymer with a high specific surface prepared by a suspension method, wherein the polyamine exists in a patch form; the polyamines contain covalently incorporated traces of thioethers (1-3 mol.% of the amino repeat units). Then, the gold precursor is adsorbed by polyamine and heated to be reduced in situ, thereby generating gold nanoclusters with uniform size. The optimization results indicate that gold nanoclusters obtained in the presence of 1mo l.% of thioether are the most efficient in catalysis. Both the patch and the thioether are helpful for inhibiting the aging of the catalyst and keeping better stability (the catalytic efficiency is not reduced after 6 times of repeated use). The supported catalytic material can be conveniently recycled and reused.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to preparation of gold nanocluster loaded by using trace thioether-assisted polyamine patches and application of gold nanocluster in catalytic reduction.
Background
Nanoclusters refer to particles having a size of 0.1-3.0 nm. Because the specific surface area is high, the surface atomic ratio is high, and the catalytic efficiency of the gold nanocluster is more prominent; meanwhile, the coating has more unique physicochemical properties such as photo-thermal property and the like. On the other hand, nanoclusters are unstable due to their large specific surface area, and many challenges exist in their preparation and use. At present, the preparation of gold nanoclusters is mainly limited to the templates with precise structures such as dendrimers, carbon organic frameworks, metal organic frameworks and specially-made mesoporous silica. However, these templates are generally expensive to synthesize, and often need to be prepared in the presence of strong ligands such as thiol or polysulfide ligands. Strong ligands often cause catalyst poisoning.
Another challenge often faced with the use of heavy metal catalytic materials as catalysts is recovery, which otherwise not only poses an environmental hazard, but is more likely to seriously impact product quality, for example, the production of many pharmaceutical intermediates involves the problem of toxic heavy metal catalyst residues. The supported method is often used to aid catalyst recovery. The loading method is a heterogeneous process, and metal nanoparticles directly generated on a carrier are often non-uniformly distributed, have large size difference and are unstable in properties. The direct production of high quality gold nanoparticles on a support is a problem that is being solved. The modulation and loading of nanoparticles such as gold platinum on inorganic carriers has been relatively widely studied, particularly in oxidation catalysis, for example, platinum nanoparticles are used for catalytic oxidation of fuel cells. In contrast, the use of support materials in highly reducing environments has been relatively less well studied, and polymeric carriers are more promising in this regard.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to design a large-scale route for preparing gold nanoclusters which are loaded by microspheres, have the size of below 3 nanometers, are uniform in size and have relatively stable properties.
The second purpose of the invention is to prepare the microsphere-supported gold nanoclusters.
A third object of the invention is the use of the nanoclusters as recyclable catalysts.
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:
(1) in the presence of a good solvent type pore-forming agent, preparing the mesoporous polymer microspheres with a large number of benzyl chloride functional groups on the surface of pores by a suspension polymerization method.
(2) Carrying out polyamine functionalization on the chlorobenzyl groups on the surfaces of the microsphere pores by using trace thioether modified low-molecular-weight branched polyethyleneimine.
(3) The gold precursor is loaded onto the polyamine by electrostatic action and immediately reduced by heating to produce the loaded gold nanoclusters in situ.
Preferably, in the step (1), the polymerization monomers are 4-vinylbenzyl chloride and divinylbenzene, and the pore-foaming agent is one or two of toluene and xylene.
Preferably, in step (1), the volume of the pore-forming agent is 40-60% of the total volume of the oil phase.
Preferably, in the step (1), the molar ratio of the 4-vinylbenzyl chloride to the divinylbenzene is 0.8-1.5: 1.
Preferably, in step (2), the branched polyethyleneimine is modified by methylthiopropanal to introduce a thioether functionality.
Preferably, in step (2), the thioether functionality is incorporated in an amount of 0.5 to 3 mol.% of the number of repeating units of the branched polyethyleneimine.
Preferably, in the step (2), the dosage of the thioether-functionalized branched polyethyleneimine is 8-25% of the mass of the mesoporous microsphere.
Preferably, in step (2), the molecular weight of the branched polyethyleneimine is 600-2000 daltons.
Preferably, in step (3), chloroauric acid or chloroauric acid salt is used as the gold precursor, 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, in the step (3), the gold precursor is heated and reduced immediately after being adsorbed by the supported polyamine at a temperature of 60 to 80 ℃.
The gold nanoclusters with small and uniform size can be obtained by the preparation method.
The catalytic material is applied to catalytic reduction of various substrates and has stable performance.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, due to the nucleation effect of thioether and the patch distribution of the ligand on the surface of the carrier, gold nanoclusters with extremely small size can be obtained, so that the proportion of surface atoms with catalytic effect is increased.
And secondly, trace thioether not only plays a role in nucleating, but also can stabilize the gold nanoclusters together with polyamine. The gold nanoclusters are still found to be quite stable in practice.
Thirdly, the method can prepare the loaded gold nanoclusters with uniform size on a large scale at low cost.
Drawings
FIG. 1 is a nitrogen adsorption curve of mesoporous polymer microspheres;
FIG. 2 is a transmission electron micrograph of gold nanoclusters (inset is their size distribution);
FIG. 3 is an XPS spectrum before and after loading a gold nanocluster on a mesoporous polymer carrier;
FIG. 4 is a graph of ultraviolet/visible light spectrum time evolution of supported gold nanoclusters for catalyzing the reduction of 4-nitrophenol;
FIG. 5 is a graph of the effect of thioether content on nanoparticle size and TOF to catalyze the reduction of 4-nitrophenol (see example 4 for a determination conditions, b for molar ratio of thioether to amino).
The present invention will be further described with reference to the following examples. The various examples are used together to illustrate catalyst preparation, conditioning, catalysis and durability and reasons.
Example 1 (mesoporous Polymer support preparation and ligand Patch introduction)
The mesoporous polymer microsphere is synthesized by a suspension polymerization method, and the pore-forming agent adopts a good solvent type so as to obtain small pore generation
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), to give an 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 dropped into the water phase under mechanical agitation at 350rpm, under nitrogenThe temperature was increased to 70 ℃ for 3 hours in an atmosphere and then to 80 ℃ for 2 hours. And (3) carrying out suction filtration to separate out microspheres, carrying out Soxhlet extraction for 12 hours by using acetone, washing for 3 times by using dilute hydrochloric acid (pH is 5-6), then carrying out immersion washing for 2 times by using ethanol, and carrying out vacuum drying at 50 ℃ to obtain the mesoporous microspheres. The specific surface area is 510m determined by nitrogen adsorption method2The average size of mesopores is 3.4nm (as shown in figure 1).
Thioether-modified polyamines
Branched polyethyleneimine (molecular weight 2000 daltons, degree of branching 60%, 0.4 g) was taken, treated with heat (60 ℃) under vacuum for half an hour and then dissolved in ethanol (15 ml). A solution of 3-methylthiopropanal (9.67mg,0.093mmol, corresponding to 1 mol.% of amino groups) in ethanol (0.93mL) was added and stirred at room temperature under nitrogen for 12 h. Taking a small amount of the mixture after vacuum drying treatment1H NMR(400MHz,CDCl3):2.04(1H，-SCH3) 2.79-2.39(132H, other hydrocarbons), 1.73(s,50H, CH)2NH,CH2NH2). The amount of thioether introduced can be judged from the relative intensities of the first two peaks as: 1 mol.% (relative to the number of nitrogen atoms of the polyamine), i.e. a completely quantitative reaction.
Modification of thioether modified polyamine to mesoporous microsphere
The mesoporous microspheres (2g) were put into the ethanol (15 ml) solution of thioether-modified polyamine, and stirred at 80 ℃ for 6h in nitrogen atmosphere. The microspheres were filtered off and washed several times with ethanol and dried. Elemental analysis gave a nitrogen content of 2.6%, from which it was concluded that the polyamine loading was 1.86mmol NH/g.
The BET method determination shows that the specific surface area of the modified thioetherified polyamine is reduced from 510 to 244m2(ii)/g, since part of the pores are blocked by the polyamine. According to theoretical calculation, when the dry polyamine exists in an idealized sphere, the diameter corresponding to the molecular weight of 2000 daltons is 1.86 nm; considering the specific surface area of the carrier, the coverage rate of the polyamine on the surface of the carrier is 26.7%. Even considering that the flexible polyamine can be deformed, the hydrophilic polyamine is difficult to lie on an oleophilic carrier, the surface coverage rate of the hydrophilic polyamine is not changed greatly, and the sulfur-fixing etherified polyamine ligand exists in a patch form on the surface of the carrier.
Example 2 (gold nanocluster preparation and loading)
Dispersing thioetherified polyamine modified mesoporous microspheres (1g,1.86mmol NH/g) in deionized water (7ml), adding HAuCl4The solution (3ml,20mM, N: Au-32: 1 (mol: mol)) was stirred vigorously at room temperature for 1min, and immediately thereafter the reaction was heated 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 ℃. The gold in the mother liquor was detected at 8ppm, indicating that almost all the gold had been loaded onto the microspheres, i.e. the gold loading of the microspheres was about 0.06 mmol/g. A small amount of microspheres are taken, finely ground and dispersed in ethanol, and then observed by a transmission electron microscope, and the grain diameter of the gold nanocluster is found to be 2.41 +/-0.26 nm (sample 3 in figure 2 and table 1). XPS analysis revealed a new presence of 84.0 and 87.7eV signals on the support, corresponding to the atomic gold signal (figure 3), indicating that the supported gold species was almost completely converted to atomic gold.
Example 3 (Regulation of gold nanocluster size by thioether content)
In example 2, polyamines having thioether contents of 0, 0.5, 2 and 3 (mol.%) respectively were substituted for polyamines having a thioether content of 1 mol.%, and the resulting gold nanocluster particle diameters were as shown in samples 1,2,4 and 5 of table 1. It can be seen that as the amount of thioether increases, the gold nanoclusters become smaller in size and become highly monodisperse. Meanwhile, as can be seen from table 1, the increase in the amount of thioether suppressed the catalytic efficiency slightly (decrease in TOF), but the catalysis was still effective. This is different from thiol-regulated gold nanoclusters, which often completely lose catalytic activity for certain reactions (s.das, a.goswami, m.hesari, j.f.al-Sharab, e.mikmekova, f.maran, t.asefa, Small 10(2014) 1473-.
Example 4 (catalytic application)
An aqueous solution (20mL) containing 4-nitrophenol (0.06mM) and sodium borohydride (0.5g) was purged with nitrogen for 15 minutes, and then sample 3 (Table 1) (0.1g) supporting gold nanoparticles was charged and stirred. The solution changed from yellow to colorless in 17 minutes, indicating that the 4-nitrophenol had been sufficiently reduced (FIG. 4). The microspheres were filtered off and used repeatedly in catalytic reduction, still reducing the yellow substrate to a colorless product within 17 minutes. No appreciable decrease in catalytic efficiency was observed after 6 repetitions of the process. The operating frequency TOF of the gold nanocluster is 354.5h according to the catalytic rate-1The operation frequency is about one order of magnitude higher than that of the common supported gold nanoparticles. In contrast, thiol-modulated gold nanoclusters no longer have a catalytic effect on many reactions (1.Dasog, M.; Hou, W.; Scott, R.W.J.Controledgrowth and catalytic activity of gold monolayered stabilizers in presence of borohydrate salts. chem.Commun.2011,47,8569-
Other catalysts were tested as well and the results showed that more or less thioether dosage reduced the catalytic efficiency as shown in table 1.
Example 5 (contribution of Patch to catalyst stability)
Further, catalyst 3 in example 4 was replaced with gold nanocatalyst (4.0 ± 1.5nm) synthesized as in the literature (j. mater. chem.a,2015,3,13519) and multiple reuse evaluations were performed keeping the dose of gold atoms the same. Both catalysts have polyamine as ligand, but the distribution of polyamine on the surface of the carrier is different, one is patch distribution and the other is continuous distribution. As a result, the literature catalyst was found to have become less efficient at the 4 th reuse and to gradually decline. This indicates that the gold nanoparticles are more stable when the ligands are distributed in patches, probably due to inhibition of migration fusion and aging of the gold atoms.
Claims (6)
1. A preparation method of a gold nanocluster loaded by trace thioether-assisted polyamine patch modulation is characterized by comprising the following steps:
(1) in the presence of a good solvent type pore-forming agent, preparing mesoporous polymer microspheres with a large number of benzyl chloride functional groups on the surfaces of pores by a suspension polymerization method;
(2) carrying out polyamine functionalization on the chlorobenzyl groups on the surfaces of the microsphere pores by using trace thioether modified low-molecular-weight branched polyethyleneimine;
(3) the gold precursor is loaded onto the polyamine by electrostatic action and immediately reduced by heating to produce the loaded gold nanoclusters in situ.
2. The preparation method according to claim 1, wherein the polymerized monomers are 4-vinylbenzyl chloride and divinylbenzene, and the pore-forming agent is one or two of toluene and xylene;
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.
3. The method of claim 1, wherein the thioether functional group is introduced in an amount of 0.5 to 3 mol.% based on the number of repeating units of the branched polyethyleneimine;
the feeding amount of the thioether functionalized branched polyethyleneimine is 8-25% of the mass of the mesoporous microsphere;
the molecular weight of the branched polyethyleneimine is 600-2000 daltons.
4. The method of claim 1, wherein chloroauric acid or chloroauric acid salt is used as the gold precursor, the pH is 6 to 9 to facilitate electrostatic adsorption, and the input amount is Au: n is 1:16 to 1:40 molar ratio, i.e. the number of nitrogen atoms is 16 to 40 times the number of gold atoms;
the gold precursor is immediately heated and reduced after being adsorbed by the loaded polyamine, and the temperature is 60-80 ℃.
5. The trace thioether-assisted polyamine patch modulated supported gold nanocluster obtained by the preparation method of any one of claims 1 to 4.
6. Catalysis of the materials of claim 5 applied to various substrates.
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