CN107349964A - A kind of preparation method of nano particle@small sized metallic organic framework materials - Google Patents
A kind of preparation method of nano particle@small sized metallic organic framework materials Download PDFInfo
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- CN107349964A CN107349964A CN201710578051.6A CN201710578051A CN107349964A CN 107349964 A CN107349964 A CN 107349964A CN 201710578051 A CN201710578051 A CN 201710578051A CN 107349964 A CN107349964 A CN 107349964A
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- nano particle
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000013384 organic framework Substances 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 23
- 230000003750 conditioning effect Effects 0.000 claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- 239000002798 polar solvent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013110 organic ligand Substances 0.000 claims description 14
- 239000002082 metal nanoparticle Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000001186 cumulative effect Effects 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- -1 polyethylene pyrrole Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims description 4
- 150000002738 metalloids Chemical class 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 229910052738 indium Inorganic materials 0.000 claims 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000013207 UiO-66 Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B01J35/393—
-
- B01J35/396—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
Abstract
The present invention relates to a kind of preparation method of nano particle@small sized metallic organic framework materials, comprise the following steps：1) polyvinyl pyrrolidon modified nano particle is prepared；2) obtained nano particle is added in MOF growth response liquid, control adds the amount of conditioning agent, obtains nano particle@small sized metallic organic framework materials.Method provided by the present invention is simple and easy; mild condition; strong applicability; the nano particle@small sized metallics organic framework materials of preparation can effectively prevent there be the characteristics of size selectivity, metal organic framework surface are short from nanoparticle activated center diffusion path while nanoparticle agglomerates, have broad application prospects in fields such as catalysis, bio-imagings.
Description
Technical field
The present invention relates to composite nano materials technical field, and especially, disclosing a kind of nano particle@small sized metallics has
The preparation method of machine frame frame material.
Background technology
Metal-organic framework material (Metal-Organic Frameworks, MOFs) is one kind by metal ion/metal
Cluster and organic ligand assemble the porous material to be formed.Because it has high-specific surface area, aperture and window size are adjustable, match somebody with somebody
The body easily design feature such as modification, has a wide range of applications in gas absorption and separation, catalysis and medicament slow release etc..In recent years
Come, composite prepared by metal organic framework (MOFs) encapsulated nanoparticles is as heterogeneous catalyst by the extensive of researcher
Concern.The nano particle of high activity, the performance that achievable one-component can not have are coated using MOF as carrier.However, tradition side
Between hundreds of to a few micrometers, limiting it at many aspects should for the MOFs of method synthesis and the composite gauge of nano particle
With therefore, it is most important developing a kind of small size MOF and nano particle composite.
The content of the invention
To solve the above problems, the present invention provides a kind of preparation side of nano particle@small sized metallic organic framework materials
Method, nano particle is prepared first, then nano particle is added in MOF growth-promoting media, controlled by the amount for adding conditioning agent
MOF nucleation rate regulates and controls the size of MOF nano-particle complexes.
A kind of preparation method of nano particle@small sized metallic organic framework materials, comprises the following steps：
1) polyvinyl pyrrolidon modified noble metal nano particles are prepared；
2) nano particle@small size carboxylic acid group's metal-organic framework materials are synthesized by the use of small molecule as conditioning agent, or
Nano particle@small size ZIF metalloid organic framework materials are synthesized by the use of organic ligand as conditioning agent.
Preferably, in step 1), the preparation method of the polyvinyl pyrrolidon modified noble metal nano particles：To 20
0.01-0.02mmol polyvinylpyrrolidones are added in the noble metal salt aqueous solution of milliliter, then add methanol constant volume to 200 millis
Rise, after polyvinylpyrrolidone stirring and dissolving, mixed solution be transferred in round-bottomed flask, be subsequently placed in oil bath pan in
50-100 DEG C of back flow reaction 1-5 hour, obtained product is rotated, then centrifuged with acetone precipitation, finally with chloroform and just
Hexane washs, and is dispersed in standby in polar solvent；The concentration of the noble metal salt aqueous solution is 0.001mol/L-0.01mol/L.
Preferably, in step 2), the preparation method of nano particle@small size carboxylic acid group's metal-organic framework materials：Will step
Polar solvent dispersion liquid, metal salt, the organic ligand of the rapid polyvinyl pyrrolidon modified noble metal nano particles 1) obtained
Mixed with conditioning agent, it is 10 milliliters to add polar solvent constant volume cumulative volume, then carries out solvent thermal reaction 12- at 100-120 DEG C
36 hours, obtained product centrifuged, then is washed with polar solvent, dried；The dosage of the noble metal nano particles is
0.005-0.01mmol, the amount of metal salts are 0.1-0.5mmol, and the amount ratio of the material of organic ligand and metal salt is 5-1：
1, the amount ratio of the material of conditioning agent and metal salt is 50-290：1；The conditioning agent is appointing in acetic acid, benzoic acid, dodecylic acid
Meaning is one or more of；Described organic ligand is terephthalic acid (TPA), amino-terephthalic acid (TPA), fumaric acid, trimesic acid
In any one or a few.
Preferably, in step 2), the preparation method of nano particle@small size ZIF metalloid organic framework materials：By step
1) polar solvent dispersion liquid, the methanol solution of metal salt of the polyvinyl pyrrolidon modified noble metal nano particles obtained
4.5 milliliters and organic ligand mixing, it is 10 milliliters to add polar solvent constant volume cumulative volume, and then 25-50 DEG C of stirring reaction 1-5 is small
When, obtained product is centrifuged, washed with polar solvent, is dried；The dosage of the noble metal nano particles is
0.0025-0.005mmol, the concentration of the methanol solution of the metal salt is 0.01mol/L-0.1mol/L, organic ligand and gold
The amount ratio for belonging to the material of salt is 5-20：1；Described organic ligand is appointing in monomethyl imidazoles, methylimidazole, benzimidazole
Meaning is one or more of.
Preferably, the precious metal salt is any one or a few in Au, Pt, Pd, Ag or Cu soluble salt.
Preferably, described metal salt is chromic nitrate, ferric nitrate, aluminum nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, nitric acid
Cerium, lanthanum nitrate, copper nitrate, magnesium chloride, manganese chloride, chromium chloride, aluminium chloride, zinc chloride, cobalt chloride, nickel chloride, copper chloride or four
Any one or a few in zirconium chloride.
Preferably, described polar solvent be selected from DMF, formamide, ethanol, methanol, chloroform, go from
One or more in sub- water.
Method provided by the present invention is simple and easy, has good versatility.While MOF encapsulated nanoparticles,
MOF size is controlled by conditioning agent regulation and control MOF nucleation rate.The MOF nano-particle complex chis of conventional method synthesis
It is very little and MOF to be reduced in size to 50nm or so with this method hundreds of to a few micrometers, its application has been widened significantly.This
The there is provided method of invention is simple and easy, mild condition, strong applicability, the nano particle@small sized metallic organic frames of preparation
Material can effectively prevent from also having size selectivity, metal organic framework surface while nanoparticle agglomerates from nanoparticle activated
The characteristics of center diffusion path is short, have broad application prospects in fields such as catalysis, bio-imagings.
Brief description of the drawings
Fig. 1 is the Pt nano particle transmission electron microscope pictures prepared in embodiment 1.
Fig. 2 is the Pt@nano-UiO-66 transmission electron microscope pictures prepared in embodiment 1.
Fig. 3 is the Pd@nano-UiO-66 transmission electron microscope pictures prepared in embodiment 1.
Fig. 4 is the powder diagram of the nano particle and MOF compounds prepared in embodiment 1.
Fig. 5 is the Pt@nano-UiO-66-NH prepared in embodiment 22Transmission electron microscope picture.
Fig. 6 is the Pt@nano-UiO-66-NH prepared in embodiment 22Powder diagram.
Fig. 7 is the Pt@nano-801 transmission electron microscope pictures prepared in embodiment 3.
Fig. 8 is the Pt@nano-801 powder diagrams prepared in embodiment 3.
Fig. 9 is the Pt@nano-ZIF-8 transmission electron microscope pictures prepared in embodiment 4.
Figure 10 is the Pt@nano-ZIF-8 powder diagrams prepared in embodiment 4.
Figure 11 is the Pt@nano-ZIF-7 transmission electron microscope pictures prepared in embodiment 5.
Figure 12 is the Pt@nano-ZIF-7 powder diagrams prepared in embodiment 5.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is carried below in conjunction with the accompanying drawings
The preparation method of the nano particle@small sized metallic organic framework materials of confession is described in detail.
Embodiment 1
1) synthesis of Pt nano particles
Chloroplatinic acid (6mM, the 20ml) aqueous solution and polyvinylpyrrolidone (0.018mmol) are mixed, then add methanol
Constant volume is to 200 milliliters, and after treating polyvinylpyrrolidone stirring and dissolving, mixed solution is transferred in 250 milliliters of round-bottomed flasks, so
After be placed in 70 DEG C of back flow reaction 3h in oil bath pan, obtained product is rotated, then centrifuged with acetone precipitation, finally uses chloroform
Washed 10 times with n-hexane, scattered standby in methyl alcohol, particle diameter is about 3nm.
2) small molecule acetic acid conditioning agent synthesis Pt@nano-UiO-66 are utilized
The polyvinyl pyrrolidon modified Pt nano particle 0.005mmol that step 1) is synthesized, zirconium chloride
0.14mmol, terephthalic acid (TPA) 0.14mmol and 0.4 milliliter of mixing of acetic acid, adding DMF constant volume cumulative volume is
10 milliliters, ultrasonic 1min be transferred to after fully dissolving in 20 milliliters of isotope bottles be placed in 120 DEG C of baking ovens carry out solvent heat it is anti-
Answer 12 hours, obtained product centrifuges, then is washed three times with DMF and ethanol respectively, drying, produces
Pt@nano-UiO-66, gained size are about 30nm.It is above-mentioned when Pt nano particles are substituted for into Pd nano particles, produce Pd@
nano-UiO-66。
For the phenogram of product as shown in 1-4, Fig. 1 is Pt nano particle transmission electron microscope pictures, and Fig. 2 is that Pt@nano-UiO-66 are saturating
Electron microscope is penetrated, Fig. 3 is Pd nano-UiO-66 transmission electron microscope pictures, and Fig. 4 is Pt nano-UiO-66, Pd nano-UiO-66 and mould
Intend powder diagram.
Embodiment 2
1) synthesis of polyvinyl pyrrolidon modified Pt nano particles is the same as embodiment 1.
2) small molecule acetic acid conditioning agent synthesis Pt@nano-UiO-66-NH are utilized2
By the pyrrolidon modified Pt nano particle 0.005mmol of foregoing synthesizing polyethylene, zirconium chloride 0.14mmol, ammonia
0.5 milliliter of mixing of base terephthalic acid (TPA) 0.14mmol and acetic acid, it is 10 milliliters to add DMF constant volume cumulative volume,
Ultrasonic 1min, which is transferred to after fully dissolving in 20 milliliters of isotope bottles, to be placed in carrying out solvent thermal reaction 36h in 120 DEG C of baking ovens, is obtained
The product arrived centrifuges, then is washed three times with DMF and ethanol respectively, drying, produces Pt@nano-UiO-
66-NH2, gained size is about 25nm.
For the phenogram of product as shown in 5-6, Fig. 5 is Pt@nano-UiO-66-NH2 transmission electron microscope pictures, and Fig. 6 is Pt@nano-
UiO-66-NH2 powder diagrams.
Embodiment 3
1) synthesis of polyvinyl pyrrolidon modified Pt nano particles is the same as embodiment 1.
2) acetic acid conditioning agent synthesis Pt@nano-801 are utilized
By foregoing synthesizing polyethylene pyrrolidon modified Pt nano particle 0.005mmol, zirconium chloride 0.14mmol, instead
0.5 milliliter of mixing of butene dioic acid 0.14mmol and acetic acid, it is 10 milliliters to add DMF constant volume cumulative volume, ultrasound
1min, which is transferred to after fully dissolving in 20 milliliters of isotope bottles, to be placed in carrying out solvent thermal reaction 24h in 120 DEG C of baking ovens, is obtained
Product centrifuges, then is washed three times with DMF and ethanol respectively, drying, produces Pt@nano-801, gained
Size is about 30nm.
For the phenogram of product as shown in 7-8, Fig. 7 is Pt@nano-801 transmission electron microscope pictures, and Fig. 8 is Pt@nano-801 powder
Diffraction pattern.
Embodiment 4
1) synthesis of polyvinyl pyrrolidon modified Pt nano particles is the same as embodiment 1.
2) conditioning agent synthesis Pt@nano-ZIF-8 are used as by the use of itself part methylimidazole
By foregoing synthesizing polyethylene pyrrolidon modified Pt nano particles 0.0025mmol, 0.055mol/L zinc nitrate
4.5 milliliters of methanol solution and methylimidazole 2mmol are mixed, and it is 10 milliliters to add methanol constant volume cumulative volume, and mixed liquor normal temperature stirs
Reaction 1h is mixed, obtained product is centrifuged, respectively washed twice with methanol and ethanol, dries, produces Pt@nano-
ZIF-8。
For the phenogram of product as shown in 9-10, Fig. 9 is Pt@nano-ZIF-8 transmission electron microscope pictures, and Figure 10 is Pt@nano-
ZIF-8 powder diagrams.
Embodiment 5
1) synthesis of polyvinyl pyrrolidon modified Pt nano particles is the same as embodiment 1.
2) conditioning agent synthesis Pt@nano-ZIF-7 are used as by the use of itself part benzimidazole
By foregoing synthesizing polyethylene pyrrolidon modified Pt nano particles 0.0025mmol, 0.02mol/L zinc nitrate
4.5 milliliters of methanol solution and benzimidazole 0.65mmol are mixed, and it is 10 milliliters to add DMF constant volume cumulative volume,
Mixed liquor stirring at normal temperature reacts 5h, and obtained product is centrifuged, with N, N dimethyl formyl and ethanol respectively washing two
It is secondary, drying, produce Pt@nano-ZIF-7.
For the phenogram of product as shown in 11-12, Figure 11 is Pt@nano-ZIF-7 transmission electron microscope pictures, and Figure 12 is Pt@nano-
ZIF-7 powder diagrams.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, but the invention is not limited in this.For those skilled in the art, the essence of the present invention is not being departed from
In the case of refreshing and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of nano particle@small sized metallic organic framework materials, it is characterised in that comprise the following steps：
1) polyvinyl pyrrolidon modified noble metal nano particles are prepared；
2) nano particle@small size carboxylic acid group's metal-organic framework materials are synthesized by the use of small molecule as conditioning agent, or utilized
Organic ligand synthesizes nano particle@small size ZIF metalloid organic framework materials as conditioning agent.
2. the preparation method of nano particle@small sized metallic organic framework materials according to claim 1, its feature exist
In, in step 1), the preparation method of the polyvinyl pyrrolidon modified noble metal nano particles：To 20 milliliters of noble metal
0.01-0.02mmol polyvinylpyrrolidones are added in saline solution, then add methanol constant volume to 200 milliliters, polyethylene pyrrole
After pyrrolidone stirring and dissolving, mixed solution is transferred in round-bottomed flask, is subsequently placed in oil bath pan in 50-100 DEG C of backflow
1-5 hours are reacted, obtained product is rotated, then are centrifuged with acetone precipitation, are finally washed with chloroform and n-hexane, are disperseed
It is standby in polar solvent；The concentration of the noble metal salt aqueous solution is 0.001mol/L-0.01mol/L.
3. the preparation method of nano particle@small sized metallic organic framework materials according to claim 2, its feature exist
In, in step 2), the preparation method of nano particle@small size carboxylic acid group's metal-organic framework materials：Step 1) is obtained poly-
Polar solvent dispersion liquid, metal salt, organic ligand and the conditioning agent mixing of the noble metal nano particles of vinylpyrrolidone modification,
It is 10 milliliters to add polar solvent constant volume cumulative volume, then carries out solvent thermal reaction 12-36 hours at 100-120 DEG C, obtains
Product centrifuges, then is washed with polar solvent, dries；The dosage of the noble metal nano particles is 0.005-0.01mmol,
The amount of metal salts is 0.1-0.5mmol, and the amount ratio of the material of organic ligand and metal salt is 5-1：1, conditioning agent and metal
The amount ratio of the material of salt is 50-290：1.
4. the preparation method of nano particle@small sized metallic organic framework materials according to claim 2, its feature exist
In, in step 2), the preparation method of nano particle@small size ZIF metalloid organic framework materials：The poly- second that step 1) is obtained
The polar solvent dispersion liquid of noble metal nano particles, 4.5 milliliters of the methanol solution of metal salt and organic of alkene pyrrolidone modification
Part mixes, and it is 10 milliliters to add polar solvent constant volume cumulative volume, then 25-50 DEG C of stirring reaction 1-5 hour, the production that will be obtained
Thing is centrifuged, and is washed with polar solvent, drying；The dosage of the noble metal nano particles is 0.0025-
0.005mmol, the concentration of the methanol solution of the metal salt are 0.01mol/L-0.1mol/L, organic ligand and metal salt thing
The amount ratio of matter is 5-20：1.
5. the preparation method of nano particle@small sized metallic organic framework materials according to claim 2, its feature exist
In the precious metal salt is any one or a few in Au, Pt, Pd, Ag or Cu soluble salt.
6. the preparation method of nano particle@small sized metallic organic framework materials according to claim 3, its feature exist
In the conditioning agent is any one or a few in acetic acid, benzoic acid, dodecylic acid；Described organic ligand is to benzene two
Any one or a few in formic acid, amino-terephthalic acid (TPA), fumaric acid, trimesic acid.
7. the preparation method of the nano particle@small sized metallic organic framework materials according to claim 3 or 4, its feature
It is, described metal salt is chromic nitrate, ferric nitrate, aluminum nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, cerous nitrate, lanthanum nitrate, nitre
Appointing in sour copper, magnesium chloride, manganese chloride, chromium chloride, aluminium chloride, zinc chloride, cobalt chloride, nickel chloride, copper chloride or zirconium chloride
Meaning is one or more of.
8. the preparation method of nano particle@small sized metallic organic framework materials according to claim 4, its feature exist
In described organic ligand is any one or a few in monomethyl imidazoles, methylimidazole, benzimidazole.
9. the preparation method of nano particle@small sized metallic organic framework materials according to claim 8, its feature exist
In the one kind of described polar solvent in DMF, formamide, ethanol, methanol, chloroform, deionized water
It is or several.
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Application publication date: 20171117 |