CN106807446A - A kind of composites of Ag@MIL 101 and its preparation method and application - Google Patents
A kind of composites of Ag@MIL 101 and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- 239000013177 MIL-101 Substances 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- -1 by volume Substances 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims 4
- 238000005119 centrifugation Methods 0.000 claims 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 235000002597 Solanum melongena Nutrition 0.000 claims 1
- 244000061458 Solanum melongena Species 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000004690 nonahydrates Chemical class 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 23
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- Organic Chemistry (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
本发明涉及一种Ag@MIL‑101复合材料及其制备方法和应用。采用的技术方案是：将硝酸银加入到乙腈中，超声分散，并将溶液缓慢滴加到MIL‑101晶体中，得到Ag+@MIL‑101；于Ag+@MIL‑101中，加入饱和的硼氢化钠的乙醇溶液，得到Ag@MIL‑101复合材料。本发明合成的Ag@MIL‑101复合材料对环氧化反应中苯乙烯具有高效的催化活性。
The invention relates to an Ag@MIL‑101 composite material, a preparation method and application thereof. The technical scheme adopted is: add silver nitrate to acetonitrile, ultrasonically disperse, and slowly add the solution dropwise to MIL-101 crystals to obtain Ag + @MIL-101; add saturated Ag + @MIL-101 to Ag + @MIL-101 Sodium borohydride in ethanol solution to obtain Ag@MIL‑101 composites. The Ag@MIL‑101 composite material synthesized by the present invention has high catalytic activity to styrene in the epoxidation reaction.
Description
技术领域technical field
本发明属于贵金属催化有机物合成领域，具体的涉及一种以新型金属有机骨架材料(MIL-101)作为载体，使银纳米粒子负载入其中，形成一种新的Ag@MIL-101复合材料，具有选最终反应产物的能力，生成传统方法很难生成且产率很低的环氧苯乙烯。The invention belongs to the field of noble metal catalyzed organic compound synthesis, and specifically relates to a new type of metal-organic framework material (MIL-101) as a carrier, and silver nanoparticles are loaded into it to form a new Ag@MIL-101 composite material, which has The ability to select the final reaction product can generate styrene oxide which is difficult to generate and the yield is very low by traditional methods.
背景技术Background technique
环氧化物含有一个氧原子和两个碳原子组成的三元环结构。它是一类重要的有机合成中间体和化工原料，其可以通过选择性开环或官能团的转化，生成一系列有价值的化合物，广泛应用于精细化工、石油化工、制药、表面活性剂、高分子材料及电子工业等领域。但是这类反应在无催化剂条件下转化率极低。Epoxides contain a three-membered ring structure consisting of one oxygen atom and two carbon atoms. It is an important class of organic synthesis intermediates and chemical raw materials, which can generate a series of valuable compounds through selective ring opening or functional group transformation, and are widely used in fine chemicals, petrochemicals, pharmaceuticals, surfactants, high Molecular materials and electronics industry and other fields. However, the conversion rate of this type of reaction is extremely low under the condition of no catalyst.
作为催化材料家族中最为重要的一员，贵金属纳米材料一直是催化领域研究的热点，在纳米催化领域也不例外。贵金属主要是指金(Au)、银(Ag)、铂(Pt)、钯(Ag)、钌(Ru)、铑(Rh)等稀缺而昂贵的金属，是有色金属的重要组成部分。但是，单质状态的贵金属在空气状态下并不足够稳定，而且非常容易团聚，在催化反应中并不能表现出非常良好的催化性能。As the most important member of the family of catalytic materials, noble metal nanomaterials have always been a research hotspot in the field of catalysis, and the field of nanocatalysis is no exception. Precious metals mainly refer to rare and expensive metals such as gold (Au), silver (Ag), platinum (Pt), palladium (Ag), ruthenium (Ru), rhodium (Rh), and are important components of non-ferrous metals. However, noble metals in the single state are not stable enough in the air state, and are very easy to agglomerate, and cannot show very good catalytic performance in catalytic reactions.
发明内容Contents of the invention
本发明的目的在于，通过将银纳米粒子有效的负载入金属有机骨架材料中，生成一种具备孔洞结构的全新复合材料(Ag@MIL-101)。该复合材料在催化烯烃环氧化反应过程中存在选择性催化。The purpose of the present invention is to generate a new composite material (Ag@MIL-101) with a porous structure by effectively loading silver nanoparticles into a metal-organic framework material. The composite material has selective catalysis in the process of catalyzing olefin epoxidation reaction.
本发明采用的技术方案是：一种Ag@MIL-101复合材料，制备方法如下：将硝酸银加入到乙腈溶液中，搅拌30-40分钟，然后将混合后的溶液缓慢滴加到MIL-101晶体中，搅拌4-6小时，真空干燥，得到Ag+@MIL-101；于Ag+@MIL-101中，加入饱和的硼氢化钠的乙醇溶液，搅拌1-2小时，用无水乙醇洗涤，离心，110℃干燥，得到Ag@MIL-101复合材料。The technical solution adopted in the present invention is: a kind of Ag@MIL-101 composite material, the preparation method is as follows: silver nitrate is added to the acetonitrile solution, stirred for 30-40 minutes, and then the mixed solution is slowly added dropwise to MIL-101 In the crystal, stir for 4-6 hours, dry in vacuum to get Ag + @MIL-101; add saturated ethanol solution of sodium borohydride to Ag + @MIL-101, stir for 1-2 hours, wash with absolute ethanol , centrifuged, and dried at 110°C to obtain the Ag@MIL-101 composite.
上述的Ag@MIL-101复合材料，按质量比，硝酸银:MIL-101晶体＝3:1。For the above-mentioned Ag@MIL-101 composite material, according to the mass ratio, silver nitrate:MIL-101 crystal=3:1.
上述的Ag@MIL-101复合材料，所述的MIL-101晶体的制备方法如下：将九水合硝酸铬和对苯二甲酸置于水热合成反应釜中，同时加入醋酸和亚沸蒸馏水，搅拌均匀后，将水热合成反应釜放入烘箱中，于180-220℃下，反应8-10h，反应结束后，过滤去除滤液后，将固体用水和乙醇的混合溶液清洗，将清洗后的固体放入水和乙醇的混合溶液中，75-80℃静置过夜，过滤，将固体颗粒放入真空干燥箱中155-160℃真空干燥。The above-mentioned Ag@MIL-101 composite material, the preparation method of the MIL-101 crystal is as follows: put chromium nitrate nonahydrate and terephthalic acid in a hydrothermal synthesis reactor, add acetic acid and sub-boiling distilled water at the same time, stir After uniformity, put the hydrothermal synthesis reactor into an oven, and react at 180-220°C for 8-10 hours. After the reaction, remove the filtrate by filtration, wash the solid with a mixed solution of water and ethanol, and wash the solid Put it into a mixed solution of water and ethanol, let it stand overnight at 75-80°C, filter, and put the solid particles into a vacuum drying oven for vacuum drying at 155-160°C.
上述的Ag@MIL-101复合材料，所述的水和乙醇的混合溶液，按体积比，乙醇:水＝19:1。For the above-mentioned Ag@MIL-101 composite material, the mixed solution of water and ethanol has a volume ratio of ethanol:water=19:1.
上述的Ag@MIL-101复合材料在催化苯乙烯环氧化反应中的应用。方法如下：取一定量的苯乙烯和叔丁基过氧化氢，溶于乙腈中，加入上述的Ag@MIL-101复合材料，得到混合溶液，将混合溶液置于茄型反应瓶中，再向混合溶液中通氮气以排除溶液中的氧气，在密闭条件下，于80下反应8h。优选的，每1mmol苯乙烯加入5mg的Ag@MIL-101。The application of the above-mentioned Ag@MIL-101 composite material in the catalysis of styrene epoxidation reaction. The method is as follows: take a certain amount of styrene and tert-butyl hydroperoxide, dissolve them in acetonitrile, add the above-mentioned Ag@MIL-101 composite material to obtain a mixed solution, put the mixed solution in an eggplant-shaped reaction bottle, and pour it into Nitrogen was passed through the mixed solution to exclude the oxygen in the solution, and under airtight conditions, the reaction was carried out at 80 for 8 hours. Preferably, 5 mg of Ag@MIL-101 is added per 1 mmol of styrene.
本发明的有益效果：Beneficial effects of the present invention:
1.本发明合成的Ag@MIL-101复合材料，对苯乙烯环氧化反应中苯乙烯具有特殊的选择性催化活性，能增大苯乙烯的转化率，并较大量的产生环氧苯乙烯。1. The Ag@MIL-101 composite material synthesized by the present invention has special selective catalytic activity for styrene in styrene epoxidation reaction, can increase the conversion rate of styrene, and produce a large amount of epoxy styrene .
2.本发明采用MIL-101晶体作为负载贵金属银纳米粒子的金属有机骨架材料，形成新型的复合材料，本发明采用的MIL-101晶体，孔洞适中、性质稳定，既可以保证负载入其中的金属银的分散，又可以避免由于团聚、氧化等因素引起的催化剂失活。2. The present invention adopts MIL-101 crystal as the metal-organic framework material for loading precious metal silver nanoparticles to form a novel composite material. The MIL-101 crystal adopted in the present invention has moderate pores and stable properties, which can ensure that the metal loaded into it The dispersion of silver can avoid catalyst deactivation caused by factors such as agglomeration and oxidation.
3.本发明合成的Ag@MIL-101复合材料，具有良好的重复利用能力，易与反应物分离，对整个反应体系不存在干扰。3. The Ag@MIL-101 composite material synthesized by the present invention has good reusability, is easy to separate from reactants, and does not interfere with the entire reaction system.
附图说明Description of drawings
图1是模拟MIL-101、实施例1合成的MIL-101和Ag@MIL-101复合材料的XRD图。Fig. 1 is the XRD pattern of simulating MIL-101, MIL-101 synthesized in Example 1 and Ag@MIL-101 composite material.
图2是实施例1合成的Ag@MIL-101复合材料的透射电镜图。Fig. 2 is a transmission electron microscope image of the Ag@MIL-101 composite material synthesized in Example 1.
图3是本发明合成的Ag@MIL-101催化苯乙烯环氧化反应0h和8h后产物的气相图。Fig. 3 is the gas phase diagram of the product after 0h and 8h of the styrene epoxidation reaction catalyzed by Ag@MIL-101 synthesized by the present invention.
具体实施方式detailed description
实施例1Ag@MIL-101复合材料Embodiment 1Ag@MIL-101 composite material
(一)制备方法(1) Preparation method
1.MIL-101晶体的制备1. Preparation of MIL-101 crystals
称取800mg九水合硝酸铬和328mg对苯二甲酸于25mL水热合成反应釜中，同时加入1.5mL的醋酸(99.5％)和10mL亚沸蒸馏水，用搅拌转子密闭搅拌30min，搅拌均匀后取出转子，将水热合成反应釜放入200℃烘箱中反应8h。反应结束后，过滤去除滤液后，将固体用水和乙醇的混合溶液(乙醇：水＝19：1)清洗，将清洗后的固体放入10mL的水和乙醇的混合溶液中，80℃放置24h，过滤，得到MIL-101晶体。Weigh 800mg of chromium nitrate nonahydrate and 328mg of terephthalic acid into a 25mL hydrothermal synthesis reaction kettle, add 1.5mL of acetic acid (99.5%) and 10mL of sub-boiling distilled water at the same time, and stir with a stirring rotor for 30min, and take out the rotor after stirring evenly , put the hydrothermal synthesis reactor into an oven at 200°C for 8 hours. After the reaction, remove the filtrate by filtration, wash the solid with a mixed solution of water and ethanol (ethanol:water=19:1), put the washed solid into a mixed solution of 10 mL of water and ethanol, and place it at 80°C for 24h. Filter to obtain MIL-101 crystals.
2.MIL-101晶体的活化2. Activation of MIL-101 crystals
将MIL-101晶体放入真空干燥箱中160℃真空干燥12h，得到活化后的MIL-101晶体，氮气条件下保存。The MIL-101 crystal was put into a vacuum drying oven at 160° C. for 12 hours in vacuum to obtain the activated MIL-101 crystal, which was stored under nitrogen.
3.Ag@MIL-101复合材料的制备3. Preparation of Ag@MIL-101 composite
准确称取300mg(1.77mmol)硝酸银固体颗粒加入到8mL乙腈中，搅拌30min，使硝酸银全部溶解。再将硝酸银的乙腈溶液缓慢滴加到100mg活化后的MIL-101晶体中，磁力搅拌5小时后，离心，真空干燥12小时，得到Ag+@MIL-101。Accurately weigh 300 mg (1.77 mmol) of silver nitrate solid particles into 8 mL of acetonitrile, and stir for 30 min to completely dissolve the silver nitrate. The acetonitrile solution of silver nitrate was slowly added dropwise to 100 mg of the activated MIL-101 crystal, stirred magnetically for 5 hours, centrifuged, and dried in vacuum for 12 hours to obtain Ag + @MIL-101.
于Ag+@MIL-101中，加入4mL 0.6mol/L的硼氢化钠的乙醇溶液，于室温下，搅拌1.5小时后，离心，并用乙醇溶液洗涤，100℃真空干燥，得到Ag@MIL-101复合材料，氮气条件下密封保存，备用。Add 4mL of 0.6mol/L sodium borohydride ethanol solution to Ag + @MIL-101, stir at room temperature for 1.5 hours, centrifuge, wash with ethanol solution, and dry in vacuum at 100°C to obtain Ag@MIL-101 Composite materials, sealed and stored under nitrogen conditions, for future use.
(二)检测结果(2) Test results
1.将得到的MIL-101晶体和Ag@MIL-101复合材料，分别进行XRD表征，结果如图1所示。由图1可见，本发明合成的Ag@MIL-101复合材料在合成过程中晶体结构没有破坏。1. The obtained MIL-101 crystal and Ag@MIL-101 composite were characterized by XRD respectively, and the results are shown in Figure 1. It can be seen from Figure 1 that the crystal structure of the Ag@MIL-101 composite material synthesized by the present invention is not destroyed during the synthesis process.
2.将得到的Ag@MIL-101复合材料进行透射电子显微镜表征和X射线衍射仪表征，透射电子显微镜表征结果如图2所示，由图2可见，图2中黑点表示成功负载入MIL-101晶体中的银纳米粒子，且这些负载入其中的银纳米粒子大小在2.5nm左右，粒径比较均匀。本发明合成的Ag@MIL-101复合材料中，还原后的银纳米粒子被完全负载入金属有机骨架材料的孔洞当中，尺寸单一且分布均匀。2. The obtained Ag@MIL-101 composite material was characterized by transmission electron microscope and X-ray diffractometer. The results of transmission electron microscope characterization are shown in Figure 2. It can be seen from Figure 2 that the black dots in Figure 2 indicate that it has been successfully loaded into MIL -101 silver nanoparticles in the crystal, and the size of these silver nanoparticles loaded into it is about 2.5nm, and the particle size is relatively uniform. In the Ag@MIL-101 composite material synthesized by the present invention, the reduced silver nanoparticles are completely loaded into the pores of the metal-organic framework material, and the size is single and the distribution is uniform.
实施例2Ag@MIL-101复合材料选择性催化苯乙烯环氧化反应Example 2 Ag@MIL-101 composite material selectively catalyzes styrene epoxidation reaction
方法如下：将10mmol(1.14ml)苯乙烯、30mmol(2.873ml)叔丁基过氧化氢溶于5ml乙腈溶液中，分别加入实施例1制备的50mg Ag@MIL-101复合材料和50mg MIL-101材料，然后分别置于20mL茄型反应瓶中，连接冷凝装置，将反应装置固定好，先将长针头伸入液面以下，通10min氮气，排除掉溶液中含有的氧气，再将针头拔出，使整个体系处于密闭状态，在温度80℃下反应8h后，分别取反应液进行气相色谱进行监测，结果如图3所示。The method is as follows: Dissolve 10mmol (1.14ml) styrene and 30mmol (2.873ml) tert-butyl hydroperoxide in 5ml acetonitrile solution, add 50mg Ag@MIL-101 composite material prepared in Example 1 and 50mg MIL-101 Then place the materials in 20mL eggplant-shaped reaction bottles, connect the condensing device, fix the reaction device, first extend the long needle below the liquid surface, and pass nitrogen for 10 minutes to get rid of the oxygen contained in the solution, and then pull out the needle , keep the whole system in an airtight state, and after reacting at a temperature of 80°C for 8 hours, the reaction liquids were taken and monitored by gas chromatography, and the results are shown in Figure 3 .
图3为本发明合成的Ag@MIL-101在反应0h和8h后产物的气相图，0h气相图上面的峰a表示为反应物苯乙烯，8h气相图上面有一个明显的峰b，峰b即为最终产物环氧苯乙烯，反应24h后经气相色谱检测，苯乙烯的转化率为25.2％，环氧苯乙烯的选择性为80.5％。Figure 3 is the gas phase diagram of the Ag@MIL-101 synthesized by the present invention after 0h and 8h of reaction. It is the final product of epoxy styrene, and after 24 hours of reaction, the conversion rate of styrene is 25.2% and the selectivity of epoxy styrene is 80.5%.
本发明的Ag@MIL-101复合材料能够选择性催化苯乙烯反应，生成大量产物环氧苯乙烯，副产物少而且选择性较高，有利于反应物的高效利用，并且方便产物的提纯与分离。The Ag@MIL-101 composite material of the present invention can selectively catalyze the reaction of styrene to generate a large amount of product epoxy styrene, with few by-products and high selectivity, which is conducive to the efficient utilization of reactants and facilitates the purification and separation of products .
实施例3Ag@MIL-101复合材料重复性试验Example 3Ag@MIL-101 composite material repeatability test
将实施例2反应结束后，分离出Ag@MIL-101复合材料，重复实施例2的实验4次。通过重复试验，反应五次Ag@MIL-101复合材料对该反应的产率变化不大，仍然具有良好的催化活性和选择性。证明本发明合成的Ag@MIL-101复合材料具有较好重复利用能力，存在潜在的应用价值。After the reaction in Example 2 was completed, the Ag@MIL-101 composite material was isolated, and the experiment in Example 2 was repeated 4 times. Through repeated experiments, the yield of the Ag@MIL-101 composite reacted five times did not change much, and still had good catalytic activity and selectivity. It proves that the Ag@MIL-101 composite material synthesized by the present invention has good reusability and potential application value.
Claims (7)
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| CN108043462A (en) * | 2017-11-27 | 2018-05-18 | 辽宁大学 | A kind of Ag/UiO-66-NH2Composite material and its preparation method and application |
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| CN109395697A (en) * | 2018-11-16 | 2019-03-01 | 武汉理工大学 | A kind of preparation method carrying silver-colored adsorbent and its application in water body containing iodine |
| CN110237816A (en) * | 2019-06-13 | 2019-09-17 | 江苏科技大学 | Preparation method and application of a silver nitrate-modified metal-organic framework adsorption material |
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