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
- 239000010931 gold Substances 0.000 title claims abstract description 55
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 53
- 229920000768 polyamine Polymers 0.000 title claims abstract description 34
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000004005 microsphere Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 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 group O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003361 porogen Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004803 chlorobenzyl group Chemical group 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000003446 ligand Substances 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
本发明涉及一种微量硫醚辅助多胺补丁调制负载金纳米簇及其催化应用。本发明仅采用补丁状的、弱的多配体就能制备，且金纳米簇的活性相对于强配体对应物更高。首先，在悬浮法制备的高比表面介孔聚合物表面共价修饰上支化多胺，多胺以补丁形式存在；多胺上含有共价引入的微量硫醚(氨基重复单元的1‑3mo l.％)。然后利用多胺吸附金前体并加热就地还原，从而生成尺寸均匀的金纳米簇。优化结果表明1mo l.％的硫醚存在下获得的金纳米簇催化效率最高。补丁和硫醚均有助于抑制催化剂老化，保持较好的稳定性(重复使用6次内催化效率未降低)。该负载催化材料可以方便回收并反复使用。
The invention relates to a trace amount of sulfide-assisted polyamine patch modulating and loading gold nanoclusters and its catalytic application. The present invention can be prepared using only patchy, weak polyligands, and the gold nanoclusters are more active relative to their strong ligand counterparts. First, branched polyamines were covalently modified on the surface of the high specific surface mesoporous polymer prepared by the suspension method, and the polyamines existed in the form of patches; l.%). The gold precursors were then adsorbed by polyamines and reduced in situ by heating, resulting in uniformly sized gold nanoclusters. The optimization results showed that the gold nanoclusters obtained in the presence of 1 mol.% thioether had the highest catalytic efficiency. Both patch and thioether help to inhibit catalyst aging and maintain good stability (catalytic efficiency does not decrease within 6 times of repeated use). The supported catalytic material can be easily 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)
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