WO2017181380A1 - Silver nanoparticle-composite fabric-supported catalyst, and use thereof - Google Patents
Silver nanoparticle-composite fabric-supported catalyst, and use thereof Download PDFInfo
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- WO2017181380A1 WO2017181380A1 PCT/CN2016/079853 CN2016079853W WO2017181380A1 WO 2017181380 A1 WO2017181380 A1 WO 2017181380A1 CN 2016079853 W CN2016079853 W CN 2016079853W WO 2017181380 A1 WO2017181380 A1 WO 2017181380A1
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- reaction
- catalyst
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- reduction
- composite textile
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052709 silver Inorganic materials 0.000 title abstract description 8
- 239000004332 silver Substances 0.000 title abstract description 7
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004753 textile Substances 0.000 claims description 52
- 238000006722 reduction reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 10
- 239000011943 nanocatalyst Substances 0.000 claims description 10
- 150000002828 nitro derivatives Chemical class 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- SSHIVHKMGVBXTJ-UHFFFAOYSA-N 1-nitronaphthalen-2-ol Chemical compound C1=CC=CC2=C([N+]([O-])=O)C(O)=CC=C21 SSHIVHKMGVBXTJ-UHFFFAOYSA-N 0.000 description 1
- IDJGRXQMAHESOD-UHFFFAOYSA-N 2-methyl-5-nitro-1h-indole Chemical compound [O-][N+](=O)C1=CC=C2NC(C)=CC2=C1 IDJGRXQMAHESOD-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- SWMFAAPTSMVULA-UHFFFAOYSA-N methyl 2-(2-nitrophenyl)acetate Chemical compound COC(=O)CC1=CC=CC=C1[N+]([O-])=O SWMFAAPTSMVULA-UHFFFAOYSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention discloses a nano silver composite textile catalyst and an application thereof.
- Nanoparticle materials have begun to be used in catalytic reactions due to their ultra-high surface area to volume ratio and unique catalytically active sites.
- the nanocatalyst has very good catalytic performance, the dispersed nanomaterial is very easy to agglomerate in the reaction solution, so that it cannot be effectively used; at the same time, after the end of the chemical, the recovery of the catalyst is a great challenge.
- centrifugation is often used, which causes agglomeration of the nanoparticles, so that the secondary catalytic efficiency of the nanoparticles is rapidly reduced.
- Aromatic amino compounds are an extremely important organic raw material widely used in the production of dyes, pharmaceuticals, agrochemicals, additives, surfactants, textile auxiliaries, chelating agents, polymers, and flame retardants.
- the preparation of aromatic amines mainly includes condensation preparation of amino group-containing compounds, reduction of nitro compounds, and the like.
- the reduction of aromatic nitro compounds to the corresponding amino compounds is a common method for the preparation of aromatic amines in fine chemical production.
- the preparation of aromatic amines by nitro reduction is widely used because of its simple operation and easy availability of raw materials.
- the main methods for achieving this process include: (1) catalytic hydrogenation; (2) metal reduction; (3) hydrazine hydrate reduction; and (4) electrochemical reduction.
- the above methods require relatively cumbersome and demanding reaction conditions.
- the ester reduction reaction to prepare alcohol compounds is quite important in chemical synthesis.
- the current common method is to use lithium tetrahydrogen aluminum to reduce esters in an anhydrous high temperature environment. However, this method is harsh and post-processing is dangerous, and is not suitable for large-scale applications.
- the object of the present invention is to overcome the deficiencies of the prior art and to provide a nano-silver composite textile catalyst and its application.
- a nanocatalyst consisting of nano silver supported on the surface of a textile material.
- the method for preparing the above nanocatalyst comprises the steps of: washing and drying the textile material in deionized water, then placing it in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane, dipping; taking out the textile material and using The deionized water is washed, and the textile material is placed in a 5 mM sodium borohydride aqueous solution at room temperature, immersed, washed, and dried to obtain a nanosilver composite textile catalyst.
- the concentration of the silver nitrate is 2.72 mM, and the temperature of the first immersion is 60 °C.
- the above nanocatalyst is used as a catalyst for a reduction reaction.
- the reduction reaction refers to a reduction reaction of a nitro compound or an ester compound.
- the present invention has the following beneficial effects: the nano silver composite textile catalyst of the present invention, the nano silver particles are supported on the surface of the textile fiber by in-situ growth method, and the nano silver particles are between 1-50 nm;
- the nano-silver composite textile material exhibits good catalytic performance, and can rapidly reduce the nitro compound and the ester compound at room temperature, thereby effectively solving the severe conditions for the reduction reaction of the current ester compound;
- the nano-silver composite textile catalyst is easy It is a new type of catalytic technology because it is prepared, recyclable, cheap, and can be used for large-scale production.
- the nano silver composite textile catalyst of the invention can rapidly reduce the aromatic nitro compound to an aromatic amine at room temperature, and can reduce the ester compound to alcohol at room temperature with an aqueous solvent as a reaction medium. Scale and industrial production. In addition, the nanosilver composite textile catalyst of the present invention can also be recycled.
- Figure 1 Electron micrograph of nano-silver composite textile catalyst; A and B: natural cotton textile; C and D: nano-silver composite textile.
- FIG. 1 Recycling of nanosilver composite textile catalysts.
- the nano silver composite textile catalyst is prepared by a one-step in-situ growth synthesis method.
- White cotton textiles are first washed and dried in a deionized water environment.
- 43 g of water-washed cotton was placed in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane (water temperature: 60 ° C, AgNO 3 concentration: 2.72 mM), and immersed for 10 minutes; the sample was taken out and washed with deionized water.
- the sample was placed in a 5 mM aqueous sodium borohydride solution at room temperature and immersed for 10 minutes. It was observed that the cotton cloth gradually changed from white to yellow, indicating the formation of nano silver particles on the textile, followed by subsequent washing and baking.
- a nanosilver composite textile catalyst can be obtained by a dry process.
- the nano silver particles are about 10 nm, which are uniformly distributed on the surface of the textile fiber.
- Example 2 Nanosilver composite textile catalyzed reduction of nitro compounds
- Example 1 Taking the nano-silver composite textile of Example 1 as a catalyst, we first tried to catalyze the reduction reaction of nitrophenol. Specifically, 0.2 mmol of 4-nitrophenol, 1 mmol of NaBH 4 and 2 cm 2 of a nanosilver composite textile catalyst were mixed in a solution of THF/H 2 O (1 ml/1 ml) at room temperature, and it was found by tracking the reaction. The 4-nitrophenol can be reduced to 4-aminophenol in 3 hours; at the same time, our negative control test showed that no reaction was carried out without adding a nanosilver composite textile catalyst in the reaction system (other reaction conditions were the same).
- Reaction conditions 0.2 mmol of substrate, 1 mmol of NaBH 4 and 2 cm 2 of nanosilver composite textile catalyst were stirred in a mixture of THF/H 2 O (1 ml / 1 ml) at room temperature, and the progress of the reaction was followed by TLC.
- a TLC was traced to the end of the reaction;
- b purified yield.
- c The reaction was carried out at 100 °C.
- d The reaction did not end after 12 hours, and the purification of the product was stopped.
- Example 3 Recycling of a nitro compound by a nano-silver composite textile catalyst
- nano-silver composite textile catalysts are recycled.
- 2-methyl-5-nitro-1H-indole as substrate (due to its reduction products and substrates). It is easy to separate and purify on the chromatogram).
- ICP-MS inductively coupled plasma analysis
- Example 4 Nanosilver composite textile catalyzed reduction of a large amount of nitro compounds
- ester compounds As we mentioned in the background introduction, the reduction reaction of ester compounds is a huge challenge. We have tried the reduction reaction of multiple ester compounds as shown in Table 3 using nano silver composite textile catalyst. These ester compounds can be rapidly reduced to the corresponding alcohol products, and are a novel preparation method of an alcohol compound.
Abstract
A silver nanoparticle-composite fabric-supported catalyst, and use thereof. Silver nanoparticles are carried on the surface of fabric fibers by means of an in-situ growth method, and are in a range of 1-50 nm. The silver nanoparticle-composite fabric-supported catalyst enables reduction of an aromatic nitro compound into an aromatic amine, and enables, in a condition of an aqueous solvent being a reaction medium, reduction of an ester into an alcohol. The silver nanoparticle-composite fabric-supported catalyst can be recycled and reused.
Description
本发明公开了一种纳米银复合纺织催化剂及其应用。The invention discloses a nano silver composite textile catalyst and an application thereof.
纳米颗粒材料因其具有超高的表面积/体积比及独特的催化活性位点，其已开始被用于催化反应中。然而，尽管纳米催化剂具有非常好的催化效能，分散的纳米材料在反应液中非常容易团聚造成其不能被有效使用；同时，在化学结束后，催化剂的回收又是一项很大的挑战，在回收的过程中，常常会采用离心法，其会造成纳米颗粒的团聚，从而使纳米颗粒的二次催化效能急速降低。我们可以看到，发展简易、可负担的纳米催化剂及其回收技术具有非常大的挑战，其中，将纳米催化剂分散、负载于固体支撑物上是一种行之有效的办法。已有的固体支撑物包括：SiO2、TiO2、ZrO2、Al2O3、石墨烯、碳纳米管等，但是这些固体支撑物对于纳米催化剂的回收也相对较为繁琐，因为这些固体支撑物常常以微米颗粒存在，通常需要采用离心法、过滤法等方法进行回收。本专利研发者长期从事催化剂与催化反应的研究，一直致力于寻找更加实用、方便、可负担的固体支撑物。我们注意到，纺织品有品类繁多、价格便宜、柔软、具有高强度、具有耐洗性能等众多优点，是一种理想的固体支撑物，发展纳米复合纺织催化剂前景广
阔。Nanoparticle materials have begun to be used in catalytic reactions due to their ultra-high surface area to volume ratio and unique catalytically active sites. However, although the nanocatalyst has very good catalytic performance, the dispersed nanomaterial is very easy to agglomerate in the reaction solution, so that it cannot be effectively used; at the same time, after the end of the chemical, the recovery of the catalyst is a great challenge. In the process of recovery, centrifugation is often used, which causes agglomeration of the nanoparticles, so that the secondary catalytic efficiency of the nanoparticles is rapidly reduced. We can see that the development of simple and affordable nanocatalysts and their recycling technologies is very challenging. Among them, dispersing and supporting nanocatalysts on solid supports is an effective method. Existing solid supports include: SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , graphene, carbon nanotubes, etc., but these solid supports are also relatively cumbersome for the recovery of nanocatalysts because of these solid supports. It is often present in micron granules and usually needs to be recovered by centrifugation, filtration or the like. This patent developer has long been engaged in the research of catalysts and catalytic reactions, and has been working hard to find more practical, convenient and affordable solid supports. We have noticed that textiles have many advantages such as various types, low price, softness, high strength, and washability. They are an ideal solid support, and the prospect of developing nano-composite textile catalysts is broad.
包含Au,Ag,Pd及Pt在内的众多纳米金属材料已展现了独特的催化效能，其中，纳米银颗粒材料作为催化剂已被应用与甲基橙、甲基蓝及硝基酚的还原反应中，展现了独特的催化功效。本发明发展了一种纳米银复合纺织催化剂，其对硝基化合物、酯类化合物展现了超高的催化效能。芳香族氨基化合物是一种极为重要的有机原料,广泛用于染料、医药、农用化学品、添加剂、表面活性剂、纺织助剂、螯合剂以及聚合物、阻燃剂等生产中。芳香胺的制备主要有含氨基的化合物缩合制备、硝基化合物的还原等。在芳香族硝基化合物还原为相应的氨基化合物是精细化工生产制备芳胺的常用方法。硝基还原制备芳胺由于其操作简便、原料便宜易得而广泛应用。实现这一过程的主要有以下方法，包括：(1)催化加氢法；(2)金属还原法；(3)水合肼还原法；(4)电化学还原法。以上方法需要较为繁琐及苛刻的反应条件。酯还原反应制备醇类化合物是化学合成上相当的重要，当前较为常见的方法是采用四氢铝锂在无水高温环境中对酯进行还原。但这种方法条件苛刻、后处理较为危险，不适用于大规模的应用。Numerous nano-metal materials including Au, Ag, Pd and Pt have demonstrated unique catalytic performance. Among them, nano-silver particles have been used as catalysts in the reduction reaction of methyl orange, methyl blue and nitrophenol. , showing a unique catalytic effect. The invention develops a nano silver composite textile catalyst which exhibits ultra-high catalytic performance for nitro compounds and ester compounds. Aromatic amino compounds are an extremely important organic raw material widely used in the production of dyes, pharmaceuticals, agrochemicals, additives, surfactants, textile auxiliaries, chelating agents, polymers, and flame retardants. The preparation of aromatic amines mainly includes condensation preparation of amino group-containing compounds, reduction of nitro compounds, and the like. The reduction of aromatic nitro compounds to the corresponding amino compounds is a common method for the preparation of aromatic amines in fine chemical production. The preparation of aromatic amines by nitro reduction is widely used because of its simple operation and easy availability of raw materials. The main methods for achieving this process include: (1) catalytic hydrogenation; (2) metal reduction; (3) hydrazine hydrate reduction; and (4) electrochemical reduction. The above methods require relatively cumbersome and demanding reaction conditions. The ester reduction reaction to prepare alcohol compounds is quite important in chemical synthesis. The current common method is to use lithium tetrahydrogen aluminum to reduce esters in an anhydrous high temperature environment. However, this method is harsh and post-processing is dangerous, and is not suitable for large-scale applications.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足，提供一种纳米银复合纺织催化剂及其应用。The object of the present invention is to overcome the deficiencies of the prior art and to provide a nano-silver composite textile catalyst and its application.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种纳米催化剂，由纳米银负载于纺织材料表面而成。
A nanocatalyst consisting of nano silver supported on the surface of a textile material.
上述纳米催化剂的制备方法，包括如下步骤：将纺织材料在去离子水中洗涤并烘干，然后置入硝酸银与3-氨基丙基三乙氧基硅烷的混合水溶液中，浸渍；取出纺织材料并用去离子水进行清洗，再将纺织材料在室温下置入5mM浓度的硼氢化钠水溶液中，浸渍，再清洗、烘干便获得纳米银复合纺织品催化剂。The method for preparing the above nanocatalyst comprises the steps of: washing and drying the textile material in deionized water, then placing it in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane, dipping; taking out the textile material and using The deionized water is washed, and the textile material is placed in a 5 mM sodium borohydride aqueous solution at room temperature, immersed, washed, and dried to obtain a nanosilver composite textile catalyst.
在上述制备方法中，所述硝酸银的浓度为2.72mM，所述第一次浸渍的温度是60℃。In the above production method, the concentration of the silver nitrate is 2.72 mM, and the temperature of the first immersion is 60 °C.
上述纳米催化剂在作为还原反应催化剂中的应用。所述还原反应是指硝基化合物或酯类化合物的还原反应。The above nanocatalyst is used as a catalyst for a reduction reaction. The reduction reaction refers to a reduction reaction of a nitro compound or an ester compound.
与现有技术相比，本发明具有如下有益效果：本发明的纳米银复合纺织催化剂，纳米银颗粒通过原位生长法被负载于纺织纤维表面，纳米银颗粒介于1-50nm之间；该纳米银复合纺织材料展现了良好的催化功效，其可在室温条件下将硝基化合物、酯类化合物快速还原，有效的解决了当前酯类化合物还原反应的苛刻条件；该纳米银复合纺织催化剂易于制备、可重复利用、价格便宜、可用于规模化生产，是一种新型的催化技术。本发明的纳米银复合纺织催化剂，可在室温下快速将芳香族硝基化合物还原为芳胺，可以在室温下，以水性溶剂为反应介质，可将酯类化合物还原为醇，这种方法易于规模化及工业化生产。另外，本发明的纳米银复合纺织催化剂还可以循环利用。Compared with the prior art, the present invention has the following beneficial effects: the nano silver composite textile catalyst of the present invention, the nano silver particles are supported on the surface of the textile fiber by in-situ growth method, and the nano silver particles are between 1-50 nm; The nano-silver composite textile material exhibits good catalytic performance, and can rapidly reduce the nitro compound and the ester compound at room temperature, thereby effectively solving the severe conditions for the reduction reaction of the current ester compound; the nano-silver composite textile catalyst is easy It is a new type of catalytic technology because it is prepared, recyclable, cheap, and can be used for large-scale production. The nano silver composite textile catalyst of the invention can rapidly reduce the aromatic nitro compound to an aromatic amine at room temperature, and can reduce the ester compound to alcohol at room temperature with an aqueous solvent as a reaction medium. Scale and industrial production. In addition, the nanosilver composite textile catalyst of the present invention can also be recycled.
图1：纳米银复合纺织催化剂电镜图片；A与B：天然棉质纺织品；C及D：纳米银复合纺织品。
Figure 1: Electron micrograph of nano-silver composite textile catalyst; A and B: natural cotton textile; C and D: nano-silver composite textile.
图2：纳米银复合纺织催化剂的循环利用。Figure 2: Recycling of nanosilver composite textile catalysts.
实施例1：纳米银复合纺织催化剂的制备与标准Example 1: Preparation and Standard of Nano Silver Composite Textile Catalyst
纳米银复合纺织催化剂采用一步法原位生长合成法制备。白色棉质纺织品首先在去离子水的环境中进行洗涤并烘干。取43克水洗棉布置入硝酸银与3-氨基丙基三乙氧基硅烷的混合水溶液中(水温：60℃，AgNO3浓度2.72mM)，浸渍10分钟；取出样品并用去离子水进行清洗，再将样品在室温下置入5mM浓度的硼氢化钠水溶液中，浸渍10分钟，可观察到棉布从白色逐渐变成黄色，显示出纳米银颗粒在纺织品上的形成，再经过后续的清洗和烘干过程便可获得纳米银复合纺织品催化剂。The nano silver composite textile catalyst is prepared by a one-step in-situ growth synthesis method. White cotton textiles are first washed and dried in a deionized water environment. 43 g of water-washed cotton was placed in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane (water temperature: 60 ° C, AgNO 3 concentration: 2.72 mM), and immersed for 10 minutes; the sample was taken out and washed with deionized water. The sample was placed in a 5 mM aqueous sodium borohydride solution at room temperature and immersed for 10 minutes. It was observed that the cotton cloth gradually changed from white to yellow, indicating the formation of nano silver particles on the textile, followed by subsequent washing and baking. A nanosilver composite textile catalyst can be obtained by a dry process.
如图1所示，所合成的纳米银复合纺织品中，纳米银颗粒约为10nm，其均匀的分布在纺织纤维的表面。As shown in Fig. 1, in the synthesized nano-silver composite textile, the nano silver particles are about 10 nm, which are uniformly distributed on the surface of the textile fiber.
实施例2：纳米银复合纺织催化硝基化合物的还原反应Example 2: Nanosilver composite textile catalyzed reduction of nitro compounds
以实施例1中的纳米银复合纺织品为催化剂，我们首先尝试了其催化硝基苯酚的还原反应。具体的：取0.2mmol 4-硝基苯酚，1mmol NaBH4及2cm2的纳米银复合纺织催化剂在室温下混合于THF/H2O(1ml/1ml)溶液中，通过对反应的跟踪可以发现，4-硝基苯酚可在3小时内还原成4-胺基苯酚；同时，我们的阴性对照试验显示在不加入纳米银复合纺织催化剂于反应体系中(其他反应条件相同)，没有反应发生。
Taking the nano-silver composite textile of Example 1 as a catalyst, we first tried to catalyze the reduction reaction of nitrophenol. Specifically, 0.2 mmol of 4-nitrophenol, 1 mmol of NaBH 4 and 2 cm 2 of a nanosilver composite textile catalyst were mixed in a solution of THF/H 2 O (1 ml/1 ml) at room temperature, and it was found by tracking the reaction. The 4-nitrophenol can be reduced to 4-aminophenol in 3 hours; at the same time, our negative control test showed that no reaction was carried out without adding a nanosilver composite textile catalyst in the reaction system (other reaction conditions were the same).
表1：纳米银复合纺织催化硝基还原反应案例Table 1: Case of nano-silver composite textile catalyzed nitro reduction
反应条件：0.2mmol底物，1mmol NaBH4以及2cm2纳米银复合纺织催化剂在THF/H2O(1ml/1ml)混合液中室温条件下搅拌，并通过TLC跟踪反应进程。a:TLC跟踪至反应结束为止；b:纯化产率。c:反应在100℃下进行。d:反应在12小时后还未有结束，停止纯化产物。Reaction conditions: 0.2 mmol of substrate, 1 mmol of NaBH 4 and 2 cm 2 of nanosilver composite textile catalyst were stirred in a mixture of THF/H 2 O (1 ml / 1 ml) at room temperature, and the progress of the reaction was followed by TLC. a: TLC was traced to the end of the reaction; b: purified yield. c: The reaction was carried out at 100 °C. d: The reaction did not end after 12 hours, and the purification of the product was stopped.
同时，我们将该反应体系应用于其他底物中，如表1所示，纳米
银复合纺织催化剂对硝基化合物的还原反应展现了良好的催化效能。4-硝基苯酚和2-硝基苯酚可在室温条件下快速还原获得产物。硝基苯的还原稍具难度，遂将其升温，便可成功还原。硝基吲哚也具有较高的活性，其可在4小时内完成还原并获取较高的纯化产率。二氢吲哚的活性相对较低，其需要10小时才能反应完成，纯化产率为91.2％。1-硝基-2-萘酚的还原效率则稍显缓慢，经过12小时后的反应，反应产率为33.5％。需要特别指出的是，针对于2‐(2‐硝基苯基)乙酸甲酯底物的还原时，不但硝基被还原为胺基，酯基也被还原为醇。At the same time, we applied the reaction system to other substrates, as shown in Table 1, nano
The reduction of the nitro compound by the silver composite textile catalyst exhibits good catalytic performance. The 4-nitrophenol and 2-nitrophenol can be rapidly reduced at room temperature to obtain a product. The reduction of nitrobenzene is somewhat difficult, and it can be successfully reduced by heating it up. Nitroguanidine also has a higher activity, which can be reduced in 4 hours and a higher purification yield is obtained. The activity of indoline is relatively low, and it takes 10 hours to complete the reaction, and the purification yield is 91.2%. The reduction efficiency of 1-nitro-2-naphthol was slightly slow, and after 12 hours, the reaction yield was 33.5%. In particular, when the reduction of the methyl 2-(2-nitrophenyl)acetate substrate is carried out, not only the nitro group is reduced to an amine group, but also the ester group is reduced to an alcohol.
实施例3：循环利用纳米银复合纺织催化剂催化硝基化合物的还原反应Example 3: Recycling of a nitro compound by a nano-silver composite textile catalyst
纳米银复合纺织催化剂的最大优势为其可以被循环使用，为了论证其可行性，我们选用2‐甲基‐5‐硝基‐1H‐吲哚为底物进行研究(因其还原产物与底物在色谱上容易分离纯化)。我们以实施例2中的标准反应条件为实验条件，我们首先通过电感偶合等离子体分析方法(ICP-MS)检测纳米银复合纺织催化反应结束后反应液中的银溢出含量，发现仅有60ppb的银在反应液中出现，其含量非常低。The biggest advantage of nano-silver composite textile catalysts is that they can be recycled. In order to demonstrate its feasibility, we chose 2-methyl-5-nitro-1H-indole as substrate (due to its reduction products and substrates). It is easy to separate and purify on the chromatogram). Taking the standard reaction conditions in Example 2 as experimental conditions, we first detected the silver spill content in the reaction solution after the end of the nano-silver composite textile catalytic reaction by inductively coupled plasma analysis (ICP-MS), and found that only 60 ppb Silver appears in the reaction solution and its content is very low.
另一方面，我们上述反应条件下评估纳米银复合纺织催化剂的可循环催化次数，我们将反应时间控制在7小时，在室温下，第一次的反应可获取产物约为70％的纯化产率，将催化剂直接从反应体系拿出后置入新的反应体系中，以此重复，如图2所示，前五次的循环，我们可以获取一致的产率，第六次的产率为59％，第七次的产率为41％。该实验可充分证明纳米银复合纺织催化剂的可充分使用性。
On the other hand, we evaluated the number of cycles of catalyzed catalysis of the nanosilver composite textile catalyst under the above reaction conditions. We controlled the reaction time to 7 hours. At room temperature, the first reaction yielded a product with a yield of about 70%. The catalyst is taken directly from the reaction system and placed in a new reaction system, which is repeated. As shown in Fig. 2, in the first five cycles, we can obtain a consistent yield, and the sixth yield is 59. %, the seventh yield was 41%. This experiment can fully prove the full usability of the nanosilver composite textile catalyst.
实施例4：纳米银复合纺织催化大量硝基化合物的还原反应Example 4: Nanosilver composite textile catalyzed reduction of a large amount of nitro compounds
基于实施例3的模型反应，我们评估2cm2的纳米银复合纺织催化剂是否可催化更大量的反应规模。如表2所示，当我们将反应底物从0.2mmol的基础上增加4倍至1mmol的情况下，24小时后的转化率其可达到87％；若反应底物的量增加到2mmol时，转化率为57.9％；最后若反应底物的量增加到5mmol时，转化率为33.3％，由此证明2cm2的纳米银复合纺织催化剂便可催化大量的硝基化合物还原反应。Based on the model reaction of Example 3, we evaluated whether a 2 cm 2 nanosilver composite textile catalyst can catalyze a larger amount of reaction scale. As shown in Table 2, when we increase the reaction substrate by 4 times to 1 mmol from 0.2 mmol, the conversion after 24 hours can reach 87%; if the amount of the reaction substrate is increased to 2 mmol, The conversion rate was 57.9%; finally, when the amount of the reaction substrate was increased to 5 mmol, the conversion rate was 33.3%, thereby demonstrating that the 2 cm 2 nanosilver composite textile catalyst can catalyze a large amount of reduction reaction of the nitro compound.
表2：纳米银复合纺织催化大量硝基还原反应Table 2: Nano-silver composite textile catalyzed a large number of nitro reduction reactions
a转化率基于NMR分析所得。a conversion was obtained based on NMR analysis.
实施例5：纳米银复合纺织催化酯类化合物的还原反应Example 5: Reduction reaction of nano-silver composite textile catalyzed ester compounds
正如我们在背景介绍里面所提到，酯类化合物的还原反应是当前的一个巨大挑战，我们运用纳米银复合纺织催化剂尝试了如表3所示的多个酯类化合物的还原反应，可以看到这些酯类化合物可被快速还原为对应的醇类产物，是一种醇类化合物的新型制备方法。As we mentioned in the background introduction, the reduction reaction of ester compounds is a huge challenge. We have tried the reduction reaction of multiple ester compounds as shown in Table 3 using nano silver composite textile catalyst. These ester compounds can be rapidly reduced to the corresponding alcohol products, and are a novel preparation method of an alcohol compound.
表3纳米银复合纺织催化酯类化合物还原反应Table 3 Nano-silver composite textile catalytic ester compound reduction reaction
a转化率基于NMR分析所得。
a conversion was obtained based on NMR analysis.
Claims (5)
- 一种纳米催化剂，其特征在于由纳米银负载于纺织材料表面而成。A nanocatalyst characterized by being supported on a surface of a textile material by nano silver.
- 权利要求1所述的纳米催化剂的制备方法，其特征在于包括如下步骤：将纺织材料在去离子水中洗涤并烘干，然后置入硝酸银与3-氨基丙基三乙氧基硅烷的混合水溶液中，浸渍；取出纺织材料并用去离子水进行清洗，再将纺织材料在室温下置入5mM浓度的硼氢化钠水溶液中，浸渍，再清洗、烘干便获得纳米银复合纺织品催化剂。The method for preparing a nanocatalyst according to claim 1, comprising the steps of: washing and drying the textile material in deionized water, and then placing a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane. Medium, impregnation; the textile material is taken out and washed with deionized water, and then the textile material is placed in a 5 mM aqueous solution of sodium borohydride at room temperature, immersed, washed, and dried to obtain a nanosilver composite textile catalyst.
- 如权利要求2所述的制备方法，其特征在于，所述硝酸银的浓度为2.72mM，所述第一次浸渍的温度是60℃。The method according to claim 2, wherein the concentration of the silver nitrate is 2.72 mM, and the temperature of the first immersion is 60 °C.
- 权利要求1所述纳米催化剂在作为还原反应催化剂中的应用。Use of the nanocatalyst of claim 1 as a catalyst for a reduction reaction.
- 如权利要求4所述的应用，其特征在于所述还原反应是指硝基化合物或酯类化合物的还原反应。 The use according to Claim 4, characterized in that the reduction reaction means a reduction reaction of a nitro compound or an ester compound.
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| CN101301608A (en) * | 2008-06-26 | 2008-11-12 | 南京大学 | Silicon dioxide supported nano-silver catalyst, preparation and use thereof |
| JP2011036748A (en) * | 2009-08-07 | 2011-02-24 | Ne Chemcat Corp | Catalyst for selectively hydrogenating aromatic nitro compound, method for producing and regenerating the catalyst, and method for selectively hydrogenating aromatic nitro compound by using the catalyst |
| CN102717094A (en) * | 2012-06-11 | 2012-10-10 | 无锡市顺业科技有限公司 | In-situ synthesis method of nanosilver |
| CN104492429A (en) * | 2014-12-16 | 2015-04-08 | 上海华谊（集团）公司 | Catalyst and method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation |
-
2016
- 2016-04-21 WO PCT/CN2016/079853 patent/WO2017181380A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301608A (en) * | 2008-06-26 | 2008-11-12 | 南京大学 | Silicon dioxide supported nano-silver catalyst, preparation and use thereof |
| JP2011036748A (en) * | 2009-08-07 | 2011-02-24 | Ne Chemcat Corp | Catalyst for selectively hydrogenating aromatic nitro compound, method for producing and regenerating the catalyst, and method for selectively hydrogenating aromatic nitro compound by using the catalyst |
| CN102717094A (en) * | 2012-06-11 | 2012-10-10 | 无锡市顺业科技有限公司 | In-situ synthesis method of nanosilver |
| CN104492429A (en) * | 2014-12-16 | 2015-04-08 | 上海华谊（集团）公司 | Catalyst and method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation |
Non-Patent Citations (1)
| Title |
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| HONGJUN LIU ET AL.: "A novel point-of-use water treatment method by antimicrobial nanosilver textile material", JOURNAL OF WATER AND HEALTH, vol. 4, no. 12, 31 December 2014 (2014-12-31), pages 671 * |
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